Detailed description of the invention
Embodiment of the present invention are described in detail hereinafter with reference to accompanying drawing.Description will be provided by following order.
1. anode
2. use the electrochemical appliance (secondary cell) of anode
The first secondary cell of 2-1. (square)
2-2. the second secondary cell (column type)
The third secondary cell of 2-3. (lamination membranous type)
1. anode
Fig. 1 shows the cross section structure of anode according to embodiments of the present invention.This anode such as fills for electrochemistry
Put such as secondary cell.This anode has anode collector 1 and provides the anode active material layers 2 in this anode collector 1, institute
State anode collector 1 and there is an opposite.
Anode collector
Anode collector 1 is preferably by having favourable electrochemical stability, favourable electric conductivity and favourable mechanical strength
Material make.The example of such material includes copper, nickel and rustless steel.Especially, copper is preferred, this is because thus obtain
Obtain high electric conductivity.
The surface of anode collector 1 is the most roughened.Thus, due to so-called Anchoring Effect (anchor effect),
The contact performance between anode collector 1 and anode active material layers 2 can be improved.In this case, will at least with sun
The rough surface of the anode collector 1 in the region that pole active material layer 2 is relative is enough.The example bag of roughening method
Include and form fine grain method by electrolysis process.Electrolysis process be by a cell by electrolysis in anode collector 1
Surface on form fine grained and depression and protruding method be provided.By the Copper Foil commonly referred to " electricity using electrolysis to be formed
Solve Copper Foil ".The method that the example of other roughening method includes the Copper Foil of rolling is carried out sandblasting.
10 mean roughness Rz on the surface of anode collector 1 are not particularly limited, but particularly preferably 1.5 μm or more
Greatly.In this case, 10 mean roughness Rz are more preferably 1.5 μm-30 μm (including two end values), more preferably 3 μm-30
μm (includes two end values), contacts spy because improving the most further between anode collector 1 with anode active material layers 2
Property.More particularly, if less than 1.5 μm, there is the probability that can not obtain sufficient contact performance.Meanwhile, if greatly
In 30 μm, there is the probability reducing contact performance.
Anode active material layers
Anode active material layers 2 such as provides on two surfaces of anode collector 1.But, anode active material layers 2
Can be provided in only on the single surface of anode collector 1.
Anode active material layers 2 can embed and deviate from the anode of electrode reaction thing such as lithium ion containing one or more
Material is as active material of positive electrode.If necessary, anode active material layers 2 can comprise it together with aforesaid anode active material
Its material such as conductive agent.
As anode material, having silicon is preferably as such material has embedding and de-as the material of constituent element
Go out the excellent ability of electrode reaction thing and therefore, it is possible to provide high-energy-density.The example of such material include silicon simple substance,
Alloy or compound, or at least partly there is the material of one or more phase.In particular it is preferred to the simple substance of silicon, alloy and
At least one in compound, more preferably elementary silicon.
" alloy " in the present invention, in addition to the alloy with two or more metallic elements, also includes having one
Or the alloy of Determination of multiple metal elements and one or more metalloid elements.Self-evident, aforementioned " alloy " in the present invention can
To have nonmetalloid.Its structure include solid solution, eutectic crystal (eutectic mixture), intermetallic compound and
Wherein two or more structures coexisted in them.
The example of silicon alloy include having in addition to silicon at least one in following elements as the alloy of constituent element.That is, described
The example of element includes stannum, nickel, copper, ferrum, cobalt, manganese, zinc, indium (In), silver, titanium, germanium, bismuth (Bi), antimony and chromium.
The example of silicon compound includes the compound having oxygen and carbon (C) in addition to silicon as constituent element.Silicon compound can be with example
As having in addition to silicon, one or more in the aforementioned elements of constituent element are described as with regard to silicon alloy.
The alloy of silicon or the example of compound include as follows.That is, its example includes SiB4、SiB6、Mg2Si、Ni2Si、
TiSi2、MoSi2、CoSi2、NiSi2、CaSi2、CrSi2、Cu5Si、FeSi2、MnSi2、NbSi2And TaSi2.It addition, its example bag
Include VSi2、WSi2、ZnSi2、SiC、Si3N4、Si2N2O、SiOv(0 < v≤2), SnOw(0 < w≤2) and LiSiO.
In addition to aforementioned silicon, active material of positive electrode the most also has oxygen as constituent element, this is because thereby inhibiting electrode
The expansion of anode active material layers 2 and contraction during reaction.In this case, at least part of oxygen is preferably combined with part silicon.Knot
Conjunction state can be the form of silicon monoxide, silicon dioxide, or the form of other metastable state.
Oxygen content in active material of positive electrode is not particularly limited, but preferably 1.5 atom %-40 atom % (include two
Individual end value), this is because the most more prevent expansion and the contraction of anode active material layers 2.More particularly, it is less than when oxygen content
During 1.5 atom %, the probability of Shortcomings expansion and contraction to prevent anode active material layers 2.Meanwhile, big when oxygen content
When 40 atom %, then can exceedingly improve resistance.It is used for together with electrolyte in the situation of electrochemical appliance at anode, anode
Active material does not include the coating being decomposed to form by electrolyte etc..That is, when the oxygen content calculated in active material of positive electrode,
Oxygen in above-mentioned coating does not counts.
The active material of positive electrode with oxygen is by such as introducing oxygen into shape in room continuously when deposition anode material
Become.Especially, if only there is no required oxygen content by introducing oxygen, it is also possible to introduce liquid (such as in room
Steam etc.) as the supply source of oxygen.
It addition, in addition to aforementioned silicon, active material of positive electrode the most also has metallic element as constituent element, this is because thus
Reduce the resistance of active material of positive electrode, and more suppression electrode reaction time the expansion of anode active material layers 2 and contraction.This
The example of the metallic element of sample includes at least one in following elements.That is, its example include ferrum, nickel, molybdenum, titanium, chromium, cobalt, copper,
Manganese, zinc, germanium, aluminum, zirconium, silver, stannum, antimony and tungsten.Metal element content in active material of positive electrode is not particularly limited.But,
Anode is in the situation of secondary cell, if this metal element content is excessive, should improve the thickness of anode active material layers 2 with
Battery capacity needed for acquisition, therefore can destroy anode active material layers 2, and anode active material layers 2 can be from anode current collector
Body 1 peels off.
Active material of positive electrode can all have metallic element, or can partly have metallic element.In this situation
In, the state of active material of positive electrode can be complete alloyed state (alloyed state), or not exclusively alloying state and
It it is the state (compound state or phase-separated state) that wherein silicon mixes mutually with metallic element.The state of active material of positive electrode can be led to
Cross such as energy-dispersion X-ray fluorescence spectrometry (EDX) to check.
Such as, by using alloying pellet as forming material or by metal material and anode in deposition anode material
Material deposits together, forms the active material of positive electrode with metallic element.
It addition, anode active material layers 2 preferably includes (at thickness direction) in layer that the height with higher oxygen content is oxygen-containing
Region and there is the low oxygen-containing region compared with low oxygen content, this is because prevent the swollen of anode active material layers 2 when electrode reaction
Swollen and shrink.Oxygen content in low oxygen content region is the least.Oxygen content in elevated oxygen level region is such as similar to
Oxygen content in above-mentioned active material of positive electrode.
In this situation, the highest oxygen-containing region is clipped between low oxygen-containing region, and the most oxygen-containing region and height contain
Oxygen region replaces and repeatedly stacking, this is because the most more prevent expansion and the contraction of anode active material layers 2.Contain low
In the alternately laminated situation in oxygen region and the oxygen-containing region of height, elevated oxygen level region and low oxygen content region alternately and are repeatedly distributed
In anode active material layers 2.
By such as introducing oxygen into when deposition anode material in room intermittently or changing the oxygen introduced in room
Amount is formed containing high oxygen-containing region and the anode active material layers in low oxygen-containing region.Self-evident, only by introducing oxygen
Can not obtain in the situation of requisite oxygen content, it is also possible in room, introduce liquid (such as steam etc.).
It is possible that the oxygen content in high oxygen-containing region differs markedly from the oxygen content in low oxygen-containing region, or high oxygen-containing district
The oxygen content in territory is not sufficiently different from the oxygen content in low oxygen-containing region.Especially, become continuously in aforementioned oxygen introduction volume
In the situation changed, oxygen content can change continuously.In the situation that oxygen introduction volume changes off and on, high oxygen-containing region and low
Oxygen-containing region becomes so-called " layer ".Meanwhile, in the situation that the introduction volume of oxygen changes continuously, high oxygen-containing region and low contain
Oxygen region becomes " lamellar (1amellar state) " rather than " layer ".In the later case, preferably oxygen content is oxygen-containing at height
Change incrementally or continuously between region and low oxygen-containing region.If oxygen content changes tempestuously, then exist and reduce ion
Diffusion property or make the probability that resistance increases.
It addition, active material of positive electrode is crystalline state, and it is little affected by the impact of oxidation.Therefore, the thing of active material of positive electrode
Rationality can deteriorate little with the working time, and the contact performance of anode active material layers 2 and anode collector 1 is hardly
Reduce.
The crystal state (crystalline state or amorphous state) of active material of positive electrode can be checked by X-ray diffraction.Especially, as
Really the analysis result of active material of positive electrode detects sharp peak, then this active material of positive electrode is crystalline state.Meanwhile, if anode is active
The analysis result of material detects broad peak, then this active material of positive electrode is amorphous state.
Diffraction maximum half-peak breadth (2 θ) in (111) crystal face of the active material of positive electrode obtained by X-ray diffraction is by spy
Definite limitation, but preferably 20 degree or less.It addition, the crystallite dimension coming from this crystal face is not particularly limited, it is particularly preferred, however, that
10nm or bigger.Thus, the physical property of active material of positive electrode deteriorated little with the working time, and electrode reaction thing
Diffusion property reduces hardly.
Active material of positive electrode is preferably attached to the surface of anode collector 1.Thus, anode active material layers 2 physics is fixed
In anode collector 1, and therefore anode active material layers 2 expands hardly when electrode reaction and shrinks.Aforementioned wording " sun
Pole active material is connected to the surface of anode collector 1 " represent that anode material is deposited directly on the surface of anode collector 1.
Therefore, in the situation being formed anode active material layers 2 by painting method, sintering method etc., active material of positive electrode is the most straight
Receive the surface of anode collector 1 in succession.In this case, active material of positive electrode is connected indirectly to anode collector 1, other
Between material (such as binding agent etc.) is in, or active material of positive electrode is only neighbouring with the surface of anode collector 1.
It is enough that active material of positive electrode is at least partly connected to the surface of anode collector 1 with it.If its at least portion
Divide and be connected to anode collector 1, be not connected to the situation on the surface of anode collector 1 compared to active material of positive electrode, change
It is apt to the contact strength of anode active material layers 2 and anode collector 1.Connect with anode collector 1 at segment anode active material
In the situation touched, anode active material layers 2 has part that wherein active material of positive electrode contacts and wherein with anode collector 1
The part that active material of positive electrode does not contacts with anode collector 1.
Not there is the situation of the wherein part that active material of positive electrode does not contacts with anode collector 1 at active material of positive electrode
In, whole active material of positive electrode contact with anode collector 1, the electronic conductivity between therefore improve.Meanwhile, in this feelings
In shape, the outlet (slack space) that during electrode reaction, anode active material layers 2 expands and shrinks in situation does not exists.Therefore, it is subject to
During consequent stress influence, anode collector 1 deformable.
Meanwhile, there are the feelings of the wherein part that active material of positive electrode does not contacts with anode collector 1 at active material of positive electrode
In shape, the outlet (slack space) that during electrode reaction, anode active material layers 2 expands and shrinks in situation exists.Therefore, by answering
The deformation of the anode collector 1 of power impact occurs hardly.Meanwhile, because exist in which active material of positive electrode not with anode current collector
The part of body 1 contact, the electronic conductivity between therefore can reducing.
In this case, active material of positive electrode 2 preferably has space.Thus, it is thus achieved that when electrode reaction, anode is lived
Property material layer 2 expands and shrinks the outlet (slack space) in situation, and therefore anode active material layers 2 expands hardly and receives
Contracting.
It addition, active material of positive electrode preferably carries out alloying with anode collector 1 in their at least part of interface.Cause
And, improve the contact strength of anode active material layers 2 and anode collector 1, and the therefore anode activity material when electrode reaction
The bed of material 2 expands hardly and shrinks.It addition, the electronics conduction thus improved between anode collector 1 and anode active material layers 2
Property." alloying " had both included that the constituent element of anode collector 1 and the constituent element of active material of positive electrode formed the situation of complete alloying, again
Situation including the mixing of the two constituent element.In later case, in its interface, the constituent element of anode collector 1 can be at sun
Spreading in the active material of pole, the constituent element of active material of positive electrode can spread in anode collector 1, or these constituent elements can be
Spread one another.
Especially, active material of positive electrode is the state of multiple granule.In this case, active material of positive electrode can have
The single layer structure that formed by single deposition step or can have the multiple structure formed by multiple deposition steps.So
And, if deposition step is relevant with high heat, then active material of positive electrode preferably has multiple structure.It is divided into some steps at deposition step
Situation in, anode collector 1 open-assembly time at high heat is shorter than the situation carrying out depositing in single deposition step.
The plurality of particulate anodes active material (anode active material particles) contains spheroidal particle and aspherical particle.
In this case, do not comprise the situation of spheroidal particle compared to anode active material particles, the anode activity when electrode reaction
Material layer 2 expands hardly and shrinks, and therefore anode collector 1 deforms hardly.More particularly, spheroidal particle due to its with
The high resistance that aspherical particle is compared, contributes to electrode reaction more hardly, and therefore spheroidal particle is several when electrode reaction
Do not expand and shrink.Thus, even if aspherical particle expands and shrinks and therefore produce internal stress when electrode reaction, but should
Internal stress is relaxed by spheroidal particle, and correspondingly anode collector 1 deforms because of the impact of internal stress hardly.
Aforementioned " spheroidal particle " is such granule, i.e. by using scanning electron microscope (SEM) with 8000 times put
When big multiplying power observes the surface of anode active material layers 2, it is possible to be recognized as the granule with spheric profile.Meanwhile, " aspherical
Grain " it is the granule in addition to aforementioned spheroidal particle, and the most such granule, i.e. by using SEM (enlargement ratio: 8000
When observing again) surface of anode active material layers 2, it is possible to be recognized as the granule with polygon or sheet profiles.
The number of spheroidal particle is not particularly limited.If comprising at least one spheroidal particle, spherical compared to not containing
The situation of granule, anode collector 1 becomes to deform hardly.But, if being helpless to the number of the spheroidal particle of electrode reaction
Excessive, then can reduce embedding and the abjection amount of electrode reaction thing.More particularly, if this anode is for secondary cell, then battery
Capacity can reduce.Therefore, the number of spheroidal particle is preferably 10pcs-200pcs (including two end values).
By using the image on 30 anode active material layers 2 surfaces of SEM (enlargement ratio: 8000 times) shooting, (SEM schemes
Picture), count the spheroidal particle number of each image, and then the count number of each image is averaged, it is thus achieved that above-mentioned ball
Shape numbers of particles.In this case, the observation scope (term of reference) carried out by SEM is 10.75 μm height and 16.00 μm
Wide.It addition, be not counted in the granule (partial contour is at the separate granule in the edge of image) that its profile is not included in an image.
In the number of counting spheroidal particle, the most only count spherical in given range of particle diameter (median size)
Grain.Thus, it is therefore prevented that by whether counting the artificial change that molecule causes, and prevent and count huge exotic mistakenly
Matter such as dust.Aforementioned given range for example, 0.1 μm-40 μm (includes two end values).Self-evident, some spheroidal particle have
There is the particle diameter less than 0.1 μm.Compared to particle diameter spheroidal particle within the above range, the most small spheroidal particle tends to several
Do not make the internal stress relaxation produced in anode active material layers 2.Therefore, in for making practically in anode active material layers 2
Stress relaxation, it is enough that attention concentrates merely on particle diameter spheroidal particle within the above range.
The particle diameter (median size) of spheroidal particle is more preferably 0.5 μm-35 μm (including two end values), this is because anode
Active material layer 2 thus expands more hardly when electrode reaction and shrinks, and the embedding of electrode reaction thing and abjection amount
Reduce hardly.More particularly, if the particle diameter of spheroidal particle (median size) is less than 0.5 μm, then spheroidal particle can be hardly
Make the internal stress relaxation in anode active material layers 2.Meanwhile, if the particle diameter of spheroidal particle (median size) is more than 35 μm, can
Reduce embedding and the abjection amount of electrode reaction thing.In this case, if this anode is for secondary cell, then battery can be reduced
Capacity.The computational methods of above-mentioned spheroidal particle particle diameter are similar to the computational methods with regard to the situation described by spheroidal particle number.
The circularity of spheroidal particle is not particularly limited.But, if circularity is too low, then spheroidal particle makes sun hardly
The internal stress relaxation produced in pole active material layer 2.Therefore, circularity is preferably 0.5-1 (including two end values).Above-mentioned spherical
The computational methods of particle circularity are similar to the computational methods with regard to the situation described by spheroidal particle number.By by spheroidal particle
Girth calculate circularity divided by the girth of the circle corresponding to this spheroidal particle area.
The shape of spheroidal particle can be any shape, but especially, at least part of spheroidal particle is preferably flat.Cause
And, it is easy to make each active material of positive electrode contact with each other and be prone to be laminated to each other, therefore increasing each anode active material particles
Between the number of contact point.Thus, improve the electronic conductivity in anode active material layers 2.Aforementioned " flat " represents spherical
Granule is in the shape extended along anode collector 1 surface direction, is i.e. the shape of approximate ellipsoidal, and this shape has along sun
Major axis on the direction on pole collector 1 surface and have with the short axle on the direction of its surface traversed by.Such pancake
Shape for example is by the characteristic shown in the situation of spraying process deposition anode material.In this case, if improving anode material
The fusion temperature of material, then anode active material particles tends in flat.
It is possible that spheroidal particle and aspherical particle are evenly distributed or are distributed unevenly.It addition, spheroidal particle
With the position relationship (vertical relation etc.) between aspherical particle is not particularly limited.As long as anode active material layers 2 is wrapped in the lump
Containing spheroidal particle and aspherical particle, then anode collector 1 deforms hardly.
Anode active material layers 2 is formed by such as spraying process.In this case, by by molten state or semi-molten
The anode material of state forms anode active material layers towards anode collector 1 injection.Thus, as it has been described above, in anode activity
In material layer 2, active material of positive electrode is crystalline state, and is connected to the surface of anode collector 1.
Anode active material layers 2 can comprise other anode material, as long as anode active material layers 2 is containing having silicon conduct
The material of constituent element is as anode material.
The example of other anode material includes to embed and deviating from electrode reaction thing and have metallic element and quasi-gold
Belong at least one in element as constituent element material (except have silicon as the material of constituent element in addition to) because such material carries
For high-energy-density.This material can be metallic element or the simple substance of metalloid element, alloy or compound, or can be at least
Part has their one or more phases.
The example of aforesaid metal elements or aforementioned metalloid element includes can be with the metal of electrode reaction thing formation alloy
Element or metalloid element.Its object lesson is at least one in lower surface element.That is, its example include magnesium, boron, aluminum, gallium,
Indium, germanium, stannum and lead (Pb).Additionally, its example includes bismuth, cadmium (Cd), silver, zinc, hafnium (Hf), zirconium, yttrium (Y), palladium (Pd) and platinum
(Pt).In particular it is preferred to stannum.Stannum has embedding and deviates from the ability of electrode reaction thing, is thus provided that high-energy-density.Tool
The example having the material of stannum includes the simple substance of stannum, alloy or compound, and at least partly has their one or more phases
Material.
The example of ashbury metal include having at least one in lower surface element as the alloy of the constituent element in addition to stannum: silicon, nickel,
Copper, ferrum, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium.The example of tin compound includes containing aerobic or carbon in addition to stannum as group
The compound of unit.Tin compound can have one or more with regard to the element described by ashbury metal as the constituent element in addition to stannum.Stannum
Alloy or the example of compound include SnSiO3, LiSnO and Mg2Sn。
Particularly as having the material of stannum, for example, it is preferable to also have in addition to the stannum as the first constituent element the second constituent element and
The material of third element, because thus improve cycle characteristics at anode in the situation of secondary cell.Under second constituent element is
At least one in surface element.That is, its example includes cobalt, ferrum, magnesium, titanium, vanadium, chromium, manganese, nickel, copper, zinc, gallium and zirconium.Its other example
Attached bag includes niobium, molybdenum, silver, indium, cerium (Ce), hafnium, tantalum, tungsten, bismuth and silicon.Third element is at least one in boron, carbon, aluminum and phosphorus.
In particular it is preferred to have stannum, cobalt and carbon containing SnCoC material, in this material, carbon content is 9.9 weight %-29.7
Weight % (includes two end values), and (Co/ (Sn+Co)) content of stannum and cobalt (includes two than preferably 20 weight %-70 weight %
Individual end value).In such compositing range, it is possible to obtain high-energy-density.Containing in SnCoC material, preferably at least part is made
Carbon for constituent element is combined with metallic element or the metalloid element as other constituent element.Thus prevent cohesion or the crystallization of stannum etc.
Change.
The material containing SnCoC has the phase comprising stannum, cobalt and carbon.Such phase is preferably low crystallization phase or Amorphous Phase.Should
Being the reaction phase can reacted with electrode reaction thing mutually, such reaction contributes to obtaining excellent characteristic mutually.Use wherein
CuK alpha ray, as in specific X-ray and situation that sweep rate is 1 degree/min, spends (including two end values) at 20 degree-50
The angle of diffraction 2 θ in, the half-peak breadth of the diffraction maximum obtained by the X-ray diffraction of this phase is preferably 1 degree or bigger.Thus, more flat
Embed and deviate from electrode reaction thing quietly, and reduce and the reactivity of electrolyte etc..In some cases, except low crystallization mutually or
Outside Amorphous Phase, containing SnCoC material, also there is the simple substance comprising every kind of element or part thereof of phase.
Other element can be comprised the most further containing SnCoC material.As other element, preferably silicon, ferrum, nickel,
Chromium, indium, niobium, germanium, titanium, molybdenum, aluminum, phosphorus, gallium or bismuth etc..Two or more in them can be had containing SnCoC material.
In addition to containing SnCoC material, further preferably have stannum, cobalt, ferrum and carbon containing SnCoFeC material.Can arbitrarily set
Composition containing SnCoFeC material.Such as, wherein iron content is set as that little composition is as follows.That is, carbon content is 9.9 weight %-
29.7 weight % (include two end values), and iron content is 0.3 weight %-5.9 weight % (including two end values), and stannum and cobalt
(Co/ (Sn+Co)) content ratio be 30 weight %-70 weight % (including two end values).It addition, such as, wherein iron content sets
The composition determining greatly is as follows.That is, carbon content is 11.9 weight %-29.7 weight % (including two end values), stannum, cobalt and ferrum
((Co+Fe)/(Sn+Co+Fe)) content ratio is 26.4 weight %-48.5 weight % (including two end values), cobalt and the (Co/ of ferrum
(Co+Fe)) content ratio is 9.9 weight %-79.5 weight % (including two end values).In such compositing range, it is thus achieved that
High-energy-density.Physical property etc. containing SnCoFeC material is similar to those containing SnCoC material aforementioned.
The example of other anode material includes material with carbon element.In material with carbon element, embedding with electrode reaction thing and deviate from relevant
Changes in crystal structure the least, thereby is achieved high-energy-density.It addition, material with carbon element acts also as conductive agent.The example of material with carbon element
Son can include the non-graphitized carbon that spacing is 0.37nm or bigger in graphitized carbon, wherein (002) face, wherein (002) face
Spacing is the graphite etc. of 0.34nm or less.More particularly, its example includes pyrolytic carbon, coke, vitreous carbon fiber, You Jiju
Compound roasting body, activated carbon and white carbon black.In above-mentioned, coke includes pitch coke, needle coke and petroleum coke.Organic polymer
Thing roasting body is obtained by roasting at a proper temperature and carbonized phenolic resin, furane resins etc..The shape of material with carbon element can
Being fibrous, spherical, granular and any shape in flakey.
It addition, the example of other anode material includes metal-oxide and polymer.Metal-oxide be such as ferrum oxide,
Ruthenium-oxide, molybdenum oxide etc..Polymer is such as polyacetylene, polyaniline, polypyrrole etc..
Self-evident, anode material can be the material beyond above-mentioned material.Furthermore it is possible to by being arbitrarily used in mixed way two
Plant or more kinds of above-mentioned anode material.
Anode active material layers 2 preferably at least part of gap location between anode active material particles has metal level.
Thus, because the metal level between anode active material particles utilizes is bonded to each other, even if anode active material layers 2 is anti-at electrode
Seasonable expansion and contraction, anode active material layers 2 is not destroyed or comes off from anode collector 1.Especially, if anode material
Material is to have interatomic bond to make a concerted effort the weak silicon material as constituent element, the most effectively prevents coming off of anode active material layers 2.Separately
Outward, because metal level plays the effect of protecting film, it is therefore prevented that with during electrode reaction activation anode active material particles contact and
The decomposition reaction caused.The example of material that its decomposition reaction obtains preventing includes being used together with anode in the secondary battery
Electrode.
As it has been described above, it is enough for providing metal level at least part of gap.If provided at least part of gap
Metal level, then obtain the foregoing advantages different from the situation not providing metal level.Self-evident, metal level is in gap
Occupation rate is the biggest, this is because improve foregoing advantages the most further.
In this case, metal level preferably covers at least part of surface of anode active material particles.Thus, anode is lived
Property material granule be prone to between metal level be combined, and this metal level is prone to play the work of protecting film in relative broad range
With.Therefore, the coverage of metal level is the widest, this is because be derived from higher effect.Especially, if position
The surface of the anode active material particles in the uppermost surface layer of anode active material layers 2 is coated with metal level, then electrolyte
Deng decomposition reaction effectively prevented.
Metal level preferably comprises the material not making metal level and electrode reaction thing react as constituent element, in order to prevent at electrode
Embedding and the abjection of electrode reaction thing is suppressed during reaction.Especially, such metal level preferably comprise ferrum, cobalt, nickel, zinc, copper and
At least one in chromium, because such element reacts with various electrode reaction thing such as lithium ions hardly, and demonstrates
Excellent combined function and defencive function.But, the material constituting metal level is not limited to metal simple-substance, and can be alloy, gold
Belong to compound or comprise the mixture of two or more in them.Self-evident, metal level can be containing except aforementioned ferrum
Metallic element outside Deng.
The thickness of metal level is not particularly limited, but in particular it is preferred to be 1nm-30000nm (including two end values), because of
For being derived from higher effect.More particularly, if thickness is less than 1nm, then metal level amount is too small, therefore exists and there is no
Enough combined function and the probability of enough defencive functions.Meanwhile, if thickness is more than 30000nm, metal level amount is excessive,
The embedding of electrode reaction thing and deviate from probability hindered when there is electrode reaction.To describe (with reference to Fig. 6 A and 6B) after a while
The definition (calculation procedure) of metal layer thickness.
The forming method of metal level is not particularly limited, but in particular it is preferred to electrolytic plating method or electroless plating method, and
And electrolytic plating method and electroless plating method can be used together, this is because thus plating film is prone to growth hence into anode
In gap between active material particle, and cover the surface of anode active material particles.
The formation process of the anode active material layers 2 comprising metal level is not particularly limited, as long as finally in anode activity
Gap between material granule is formed metal level.
For example, it is possible to, by using electroless plating method, electrolytic plating method etc. to be initially formed metal level to cover
Behind the surface of the anode material being made up of multiple granules, by spraying process deposition anode material.In this case, when anode material
When expecting to spray with molten state or semi-molten state, spray the metal level of similar state together with this.Therefore, at anode activity material
Gap between material granule forms metal level.Such as in the situation that the ideal thickness ground of metal level is relatively large, such shape
One-tenth method is effective, because if increasing the thickness of the metal level being initially formed, then adds by spraying process shape after spray coating
The thickness of the metal level become.If by use electroless plating method etc. formed on anode material surface metal level such as so that
Growth plated film, the most preferably by anode material immersing palladium chloride solution and filtering gains and form plated film.
Additionally, it is possible to, after forming multiple anode active material particles by spraying process etc., subsequently by making
Metal level is formed with electrolytic plating method etc..In this case, plated film mainly along the superficial growth of anode active material particles,
Gap between anode active material particles is formed metal level.In the situation subsequently forming metal level, it is possible to, can
Make formation anode active material particles and then form the step repeated several times of metal level.Such as, at active material of positive electrode
In the relatively large situation in ideal thickness ground of grain, such forming method is effective, because being repeatedly formed anode activity material
Material granule and metal level, and define the metal level of q.s, even if the gross thickness of anode active material particles is big.
The description of the detailed construction example of anode will be provided.
Fig. 2 A to Fig. 6 B shows the amplifier section of anode shown in Fig. 1.Fig. 2 A, 3A, 5A and 6A show the SEM in cross section
Photo (secondary electron image), Fig. 2 B, 3B, 5B and 6B show the schematic diagram of SEM image shown in Fig. 2 A, 3A, 5A and 6A.Figure
4 SEM photograph showing surface.Fig. 2 A to 4 shows the situation using elementary silicon as active material of positive electrode.Fig. 5 A to 6B shows
Show the situation that active material of positive electrode is the material with silicon and metallic element.
By such as forming anode active material layers with spraying process deposition anode material on the surface of anode collector 1
2.Anode active material layers 2 comprises multiple particulate anodes active material (anode active material particles 201).As at Fig. 2 A to 3B
Shown in, anode active material particles 201 can have the multiple structure of the thickness direction stacking along anode active material layers 2.
Additionally, as fig. 5 a and fig. 5b, anode active material particles 201 can have the surface layout along anode collector 1
Single layer structure.
Such as, as shown in Fig. 2 A to 3B, anode active material layers 2 has wherein anode active material particles 201 and sun
Pole collector 1 contact part (contact portion P1) and wherein anode active material particles 201 do not contact with anode collector 1
Part (non-contact part P2).It addition, anode active material layers 2 has multiple space 2K.
As shown in Fig. 2 A to 6B, multiple anode active material particles 201 comprise spheroidal particle 201X and aspherical particle
201Y.In the situation from surface observation anode active material layers 2, spheroidal particle 201X be rendered as having sub-circular profile or
The granule of approximate ellipsoidal profile, and aspherical particle 201Y is rendered as the granule with polygonal profile or sheet profiles.Cause
This, in SEM image, spheroidal particle 201X can clearly distinguish with aspherical particle 201Y.
At least partly aspherical particle 201Y is such as flat.I.e., as shown in Figure 3A and 3B, multiple aspherical particles
201Y comprises flat particle 201YP.Flat particle 201YP is contacted by stacking with adjacent anode active material particles 201.
In the situation that anode active material particles 201 has silicon and metallic element, such as, segment anode active material
Grain 201 has silicon and metallic element.In this case, the state of anode active material particles 201 can be alloy state
Or compound (being separated) state (SP) (AP).Only there is silicon but not there is anode active material particles 201 institute of metallic element
The state at place is elemental stage (MP).
These three crystal state (MP, AP and SP) is clearly illustrated in Fig. 5 A and Fig. 5 B.I.e., it was observed that elemental stage
(MP) anode active material particles 201 is uniform grey region.Observe the anode active material particles of alloy state (AP)
201 is flat-white region.Observe that the anode active material particles 201 of phase-separated state (SP) is for wherein grey parts and white
The region of color part mixing.
The most as shown in Figure 6A and 6B, in the anode active material layers 2 gap between anode active material particles 201
There is metal level 202.Metal level 202 is such as present in by being provided to cover the surface of anode active material particles 201
In aforementioned gap.In which case it is preferred to provide metal level 202 to cover the upper space being positioned at anode active material layers 2
Anode active material particles 201 in Ceng.At least partly metal level 202 can be the alloy containing silicon.
The definition (calculation procedure) of the thickness of metal level 202 is as follows.First, it is thus achieved that anode active material layers 2 and metal level
The SEM photograph (Fig. 6 A) in the cross section of 202, described anode active material layers 2 comprises multiple anode active material particles 202.Subsequently,
Given position in SEM photograph draws vertical line L (being perpendicular to the line on the surface of anode collector 1).Afterwards, measure and vertical line L
The distance (thickness) of the metal level 202 of traversed by.In the situation shown in Fig. 6 B, (some P1 is extremely at 3 points for metal level 202 and vertical line L
P3) traversed by.Therefore, after measuring the thickness of metal level 202 of each point, it is thus achieved that its summation.Subsequently, drafting vertical line L is being changed
Position while, by obtain metal level 202 thickness (summation) aforementioned operation repeat 50 times.In this case, can appoint
Meaning ground (randomly) changes the position drawing vertical line L.But, determine position the most regularly, preferably paint with the interval of 5 μm
Vertical line L processed.Finally, the meansigma methods of metal level 202 thickness obtained is calculated 50 times.
Such as, anode is manufactured by following operation.
First, the anode collector 1 being made up of the electrolytic copper foil etc. being roughened is prepared.Subsequently, by using spraying process to exist
On the surface of anode collector 1, deposition has silicon and as the material (as anode material) of constituent element thus forms active material of positive electrode
Layer 2.In this case, spraying melting state or the anode material of semi-molten shape body, thus on the surface of anode collector 1
Deposition anode material.Therefore, the anode active material layers 2 of formation is containing multiple crystalline state anode active material particles (spheroidal particle
And aspherical particle).Therefore, anode is completed.
In the situation being formed anode active material layers 2 by use spraying process, for instance, it is possible to by regulation anode material
Particle diameter, material quality, input quantity and fusion temperature, the amount of material supply gas, the chilling temperature etc. of base material, change
The number of spheroidal particle, its particle diameter (median size) and its circularity.
According to this anode, anode active material layers 2 has the silicon crystalline state active material of positive electrode as constituent element containing multiple
Grain.The plurality of anode active material particles comprises spheroidal particle and aspherical particle.In this case, live compared to anode
Property material is amorphous situation, and the physical property of anode active material particles deteriorated little with the working time.It addition, phase
Ratio does not comprise the situation of spheroidal particle in anode active material particles, and anode active material layers 2 is the most swollen when electrode reaction
Swollen and shrink, therefore anode collector 1 deforms hardly.Therefore, this anode can aid in the performance improving electrochemical appliance.
More specifically, at this anode in the situation of secondary cell, this anode can aid in and improves cycle characteristics and expansion characteristics.
Especially, if diffraction maximum in (111) crystal face of the anode active material particles obtained by X-ray diffraction
Half-peak breadth (2 θ) is 20 degree or less, or the crystallite dimension coming from this crystal face is 10nm or bigger, then be obtained in that higher
Effect.If it addition, the median size of spheroidal particle is 0.5 μm-35 μm (including two end values), if or spheroidal particle
Circularity is 0.5-1 (including two end values), then be obtained in that higher effect.
If additionally, it is 1.5 former that anode active material particles has the oxygen content in oxygen and anode active material particles
Sub-%-40 atom % (includes two end values), if or anode active material particles there is metallic element such as ferrum, then can
Obtain higher effect.Similarly, if anode active material layers 2 has high oxygen-containing region and low oxygen-containing region, then can obtain
Effect that must be higher.
If it addition, the surface of anode collector 1 is roughened, it is possible to improve anode collector 1 and active material of positive electrode
Contact performance between layer 2.In this case, if 10 mean roughness Rz on anode collector 1 surface be 1.5 μm or
Bigger or preferably 3 μm-30 μm (including two end values), then be obtained in that higher effect.
If it addition, the gap that anode active material layers 2 is between anode active material particles has metal level 202,
Then can improve cycle characteristics further.In this case, if metal level 202 covers anode active material particles 201
Surface, then be obtained in that higher effect.
2. use the electrochemical appliance (secondary cell) of anode
It follows that by the description of the use embodiment that provides aforesaid anode.In this description, using secondary cell as electrification
Learn the embodiment of device.It is used as follows aforesaid anode.
The first secondary cell of 2-1. (square)
Fig. 7 and Fig. 8 shows the cross section structure of the first secondary cell.Fig. 8 shows along the VIII-shown in Fig. 7
The cross section that VIII line is taken.Secondary cell described herein is wherein embedding based on the lithium ion as electrode reaction thing
With the lithium rechargeable battery taking off the capacity representing anode 22.
The overall structure of secondary cell
In this secondary cell, in battery case 11, main receiving has the cell device 20 of flat wound winding-structure.
Battery case 11 is such as square package element.As shown in Figure 8, this square potted element has and in longitudinal cross-section is
Rectangle or the shape of approximate rectangular (including partial trace).This square potted element does not merely comprise the rectangular cell of rectangular shape,
And constitute the rectangular cell of elliptical shape.That is, this square potted element represents the rectangular vessel linear element with bottom, or
Having the elliptical vessel linear element of bottom, it is respectively provided with rectangular shape or the approximation formed by being connected circular arc by straight line
The opening of rectangular shape (elliptical shape).Fig. 8 shows that battery case 11 has the situation of rectangular cross sectional shape.Including aforementioned electricity
The battery structure of pond shell 11 is so-called square structure.
Battery case 11 is made up of such as ferrum, aluminum or their alloy etc..In some cases, battery case 11 also has conduct
The effect of electrode terminal.Especially, for by utilizing the rigidity of battery case 11 (the most deformable characteristic) to prevent charging
Expanding with secondary cell during electric discharge, the ferrum of rigidity is than aluminum more preferably.In the situation that battery case 11 is fabricated from iron, battery case 11 can
To carry out plating with such as nickel etc..
It addition, battery case 11 has hollow structure, wherein one end of battery case 11 is unlimited, and another of battery case 11
End is to close.At the opening of battery case 11, connect insulation board 12 and battery cover 13, thus by airtight for the inside of battery case 11
Seal.Insulation board 12 is between cell device 20 and battery cover 13, and the screw winding side face being perpendicular to cell device 20 is arranged,
And it is made up of such as polypropylene etc..Battery cover 13 is made up of the material being such as similar to battery case 11, and can be such as battery
Shell 11 equally plays the effect of electrode terminal.
Outside at battery cover 13, it is provided that terminal board 14 is as cathode terminal.Terminal board 14 and battery cover 13 are by therebetween
Insulation shell (insulating case) 16 electric insulation in addition.Insulation shell 16 is made up of such as polybutylene terephthalate etc..
It addition, the approximate center at battery cover 13 provides through hole.Negative electrode pin 15 is inserted in this through hole and negative electrode pin is electrically connected to
Terminal board 14, and with battery cover 13 by packing ring 17 electric insulation in addition therebetween.Packing ring 17 is made up of such as insulant, and
And its surface scribbles such as Colophonium.
Adjacent edges at battery cover 13, it is provided that split valve 18 and hand-hole 19.The valve 18 that splits is electrically connected to battery cover 13.
The interior pressure making battery wherein due to internal short-circuit, external heat etc. becomes, in the situation of certain level or bigger, splitting
Valve 18 separates with battery cover 13 with pressure in release.Hand-hole is sealed by the sealing member 19A being made up of such as stainless steel ball etc.
19。
Formed by stacking negative electrode 21 and anode 22 and spacer body therebetween 23 and screw winding gained laminated body
Cell device 20.According to the shape of battery case 11, cell device 20 is flat pattern.The cathode leg 24 being made up of aluminum etc. is connected
It is connected to the end (such as, end in it) of negative electrode 21.The anode tap 25 being made up of nickel etc. is connected to the end (example of anode 22
As, its outer end).Cathode leg 24 is electrically connected to terminal board 14 by being soldered to the end of negative electrode pin 15.Welding anode draws
Line 25, and it is electrically connected to battery case 11.
Negative electrode
In negative electrode 21, such as, cathode active material 21B provides at two of the cathode current collector 21A with an opposite
On individual face.But, cathode active material 21B can be provided in only on single of cathode current collector 21A.
Cathode current collector 21A is made up of such as aluminum, nickel or rustless steel etc..
Cathode active material 21B contains one or more as active material of cathode and can embed and deviate from lithium ion
Cathode material.As required, cathode active material 21B can comprise other material such as cathode adhesive and negative electrode conduction
Agent.
As cathode material, preferably lithium-containing compound, this is because it is possible to obtain high-energy-density.Lithium-containing compound
Example include the composite oxides that there is lithium and transition metal as constituent element, containing lithium and transition metal as group
The phosphate compounds of unit.In particular it is preferred at least one comprised in cobalt, nickel, manganese and ferrum is as the change of transition metal
Compound, this is because thereby is achieved higher voltage.Its chemical formula is by such as LiXM1O2Or LiyM2PO4Represent.In this formula
In, M1 and M2 represents one or more transition metals.The value of x and y changes according to charging and discharging state, and generally
It is 0.05≤x≤1.10 and 0.05≤y≤1.10.
The example of the composite oxides with lithium and transition metal includes lithium cobalt composite oxide (LiXCoO2), lithium nickel
Composite oxides (LiXNiO2) and the lithium nickel composite oxide that represented by formula 12.There is the phosphatization of lithium and transition metal
The example of compound includes lithium iron phosphate compound (LiFePO4), ithium iron manganese phosphate compounds (LiFe1-uMnuPO4(u <
1)), this is because be derived from high battery capacity and excellent cycle characteristics.
Formula 12
LiNi11-xMxO2
In the formula, M be cobalt, manganese, ferrum, aluminum, vanadium, stannum, magnesium, titanium, strontium, calcium, zirconium, molybdenum, technetium, ruthenium, tantalum, tungsten, rhenium, ytterbium, copper,
At least one in zinc, barium, boron, chromium, silicon, gallium, phosphorus, antimony and niobium.X is 0.005 < x < 0.5.
It addition, the example of cathode material includes oxide, disulphide, chalcogenide and conducting polymer.Oxide
Example includes titanium oxide, vanadium oxide and manganese dioxide.The example of disulphide includes titanium disulfide and molybdenum sulfide.Chalcogenide
Example includes selenizing niobium.The example of conducting polymer includes sulfur, polyaniline and polythiophene.
Self-evident, cathode material can be the material in addition to above-claimed cpd.Furthermore it is possible to made by arbitrarily mixing
By two or more in above-mentioned cathode material.
The example of cathode adhesive includes synthetic rubber such as butadiene-styrene rubber, Viton and ethylene propylene diene rubber;Polymerization
Thing material such as Kynoar.Can be used alone one therein, or can use therein multiple by mixing.
The example of negative electrode conductive agent includes material with carbon element such as graphite, white carbon black, acetylene black and Ketjen black (Ketjen
black).Can be used alone such material with carbon element, or can be therein multiple by being used in mixed way.Negative electrode conductive agent is permissible
It is metal material, conducting polymer etc., as long as this material has electric conductivity.
Anode
In anode 22, such as, anode active material layers 22B provides in two of anode collector 22A with an opposite
On individual face.Anode collector 22A and anode active material layers 22B are similar to that aforesaid anode Anodic collector 1 and sun
The structure of pole active material layer 2.Anode active material layers 22B comprises spheroidal particle and aspherical particle as the plurality of anode
Active material particle.In anode 22, it is possible to embed and the chargeable capacity deviate from the anode material of lithium ion preferably greater than
The discharge capacity of negative electrode 21.
Fig. 9 shows negative electrode 21 shown in Fig. 8 and the planar structure of anode 22.In fig .9, cathode active material 21B
Forming range in negative electrode 21 shade in addition, and the forming range that anode active material layers 22B is in anode 22 is the most cloudy
Shadow.
In this secondary cell, such as, the part surface at cathode current collector 21A is provided as cathode active material 21B
Time upper (such as, along longitudinally central region), anode active material layers 22B provides the whole table in anode collector 22A
On face.That is, anode active material layers 22B provides the region relative with cathode active material 21B in anode collector 22A
In (opposed area R1) or with cathode active material 21B therein not relative to region in (non-relative region R2).This
In situation, outside anode active material layers 22B, the part provided in opposed area R1 contributes to charging and discharging reaction,
The part provided in non-relative region R2 contributes to charging and discharging reaction hardly.
Live as it has been described above, anode active material layers 22B has spheroidal particle and aspherical particle as the plurality of anode
Property material granule.But, if anode active material layers 22B expands when charging and discharging and shrinks, as a result of which it is, spherical
Grain and aspherical particle deformable or destruction.In this case, non-relative region R2 is not reacted by charging and discharging and is affected,
And keep constant forming anode active material layers 22B state immediately after.Therefore, when checking the presence or absence of spheroidal particle, grain
During footpath etc., preferably check anode active material layers 22B in non-relative region R2, this is because it is possible to well to repeat
Mode check that the presence or absence etc. of spheroidal particle does not relies on charging and discharging experience.
Spacer body
Spacer body 23 is spaced apart with anode 22 by negative electrode 21, and makes lithium ion pass through and prevent by two electrodes simultaneously
The short circuit that contact produces.Spacer body 23 is by such as being constituted many by synthetic resin (such as politef, polypropylene and polyethylene)
Pore membrane or ceramic porous membrane etc. are made.Spacer body 23 can be the lamilated body being made up of two or more perforated membranes.
Electrolyte
Electrolysis immersion as liquid electrolyte is contained in spacer body 23.Electrolyte contains solvent and is dissolved in therein
Electrolytic salt.
Solvent comprises such as one or more nonaqueous solvents such as organic solvent.Can solvent the most described below.
The example of nonaqueous solvent includes as follows.That is, its example include ethylene carbonate, propylene carbonate, butylene carbonate,
Dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, gamma-butyrolacton, gamma-valerolactone, 1,2-dimethoxy
Ethane and oxolane.Its other example includes 2-methyltetrahydrofuran, Pentamethylene oxide., DOX, 4-methyl isophthalic acid,
3-dioxolanes, 1,3-dioxane and Isosorbide-5-Nitrae-dioxane.Additionally, its example includes methyl acetate, ethyl acetate, propanoic acid first
Ester, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethylacetate and tri-methyl ethyl acetate.Additionally, its example bag
Include acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, DMF, N-Methyl pyrrolidone
With N-methyloxazolidinone.Additionally, its example includes N, N '-dimethyl imidazolone, nitromethane, nitroethane, sulfolane,
Trimethyl phosphate and dimethyl sulfoxide.
In particular it is preferred in ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and Ethyl methyl carbonate
At least one.In which case it is preferred to high viscosity (high-k) solvent (such as, DIELECTRIC CONSTANT ε >=30) such as carbon
Acid ethyl and propylene carbonate and low viscosity solvent (such as, viscosity≤1mPa s) such as dimethyl carbonate, Ethyl methyl carbonate
Combination with diethyl carbonate.Thus improve dissociation properties and the ionic mobility of electrolytic salt.
Especially, solvent preferably comprises and has halogen as the tool shown in the linear carbonate of constituent element and formula 2 shown in formula 1
There is halogen as at least one in the cyclic carbonate of constituent element.Thus, when charging and discharging on the surface of anode 22 shape
Become stable protecting film, and prevent the decomposition of electrolyte.Its content (being used alone or being used in mixed way) in a solvent is not subject to
Specific restriction, but for example, it is preferable to be 0.01 weight %-50 weight % (including two end values).R11 to R16 in formula 1 can phase
Same or different.This is equally applicable to the R17 to R20 in formula 2.
Formula 1
In the formula, R11 to R16 is hydrogen, halogen, alkyl or haloalkyl.At least one in R11 to R16 is halogen
Or haloalkyl.
Formula 2
In the formula, R17 to R20 is hydrogen, halogen, alkyl or haloalkyl.At least one in R17 to R20 is halogen
Or haloalkyl.
The type of halogen is not particularly limited, but particularly preferably fluorine, chlorine or bromine, and more preferably fluorine, this is because with
Other halogen is compared and be thereby is achieved higher effect.The number of halogen is more preferably 2 compared with 1, and also can be 3
Or more, this is because hence improve the ability forming protecting film, and define more rigidity and stable protecting film.
Therefore, the decomposition reaction of electrolyte is more prevented.
The example of the linear carbonate with halogen shown in formula 1 includes fluoromethyl methylcarbonate, double (methyl fluorides)
Carbonic ester and carbonic acid difluoromethyl methyl ester.Can be used alone one therein, or can be therein by being used in mixed way
Multiple.
The example of the cyclic carbonate with halogen shown in formula 2 includes the compound shown in following formula 2-1 to 2-21.
Can be used alone one therein, or can be therein multiple by being used in mixed way.
Formula 2-1 to 2-12
Formula 2-13 to 2-21
In particular it is preferred to the 4-fluoro-1,3-dioxolan-2-one shown in formula 2-1 or 4 shown in formula 2-3,5-bis-
Fluoro-1,3-dioxolan-2-one, and more preferably the latter.Particularly as latter compound, transisomer ratio is cis
Isomer is more preferably, this is because transisomer is easily obtained and provides high effect.
Solvent preferably comprises at least one in the cyclic carbonate with unsaturated carbon bond shown in formula 3 to formula 5.From
And, on the surface of anode 22, form stable protecting film when charging and discharging, and therefore prevent the decomposition of electrolyte.Its
The content (being used alone or being used in mixed way) in solvent is not particularly limited, but for example, it is preferable to is 0.01 weight %-10 weight %
(including two end values).
Formula 3
In the formula, R21 and R22 is hydrogen or alkyl.
Formula 4
In the formula, R23 to R26 is hydrogen, alkyl, vinyl or aryl.At least one in R23 to R26 is vinyl
Or aryl.
Formula 5
In the formula, R27 is alkylidene.
The cyclic carbonate with unsaturated carbon bond shown in formula 3 is vinylene carbonate ester compounds.Vinylene carbonate
The example of ester compounds includes following compounds.That is, its example includes vinylene carbonate (1,3-dioxole-2-
Ketone), methyl vinylene (4-methyl isophthalic acid, 3-dioxole-2-ketone) and carbonic acid ethyl vinylene (4-second
Base-1,3-dioxole-2-ketone).It addition, its example includes 4,5-dimethyl-1,3-dioxole-2-
Ketone, 4,5-diethyl-1,3-dioxole-2-ketone, 4-fluoro-1,3-dioxole-2-ketone and 4-fluoroform
Base-1,3-dioxole-2-ketone.In particular it is preferred to vinylene carbonate, this is because vinylene carbonate is prone to obtain
High effect must and be provided.
The cyclic carbonate with unsaturated carbon bond shown in formula 4 is vinyl ethylene carbonate compound.Ethylene
The example of thiazolinyl ethyl compound includes following compounds.That is, its example include vinyl ethylene carbonate (4-vinyl-
DOX-2-ketone), 4-methyl-4-vinyl-DOX-2-ketone and 4-ethyl-4-vinyl-1,3-bis-
Butyl oxide link-2-ketone.Its other example includes 4-n-pro-pyl-4-vinyl-DOX-2-ketone, 5-methyl-4-ethylene
Base-DOX-2-ketone, 4,4-divinyl-DOX-2-ketone and 4,5-divinyl-1,3-dioxy penta
Ring-2-ketone.In particular it is preferred to vinyl ethylene carbonate, this is because vinyl ethylene carbonate is easily obtained, and provide
High effect.Self-evident, all of R23 to R26 can be vinyl or aryl.Additionally, some in R23 to R26 are permissible
It is vinyl, and wherein other is aryl.
The cyclic carbonate with unsaturated carbon bond shown in formula 5 is carbonic acid methylene ethyl compound.Carbonic acid is sub-
The example of methyl ethyl compound includes following compounds.That is, its example include 4-methylene-DOX-2-ketone,
4,4-dimethyl-5-methylene-DOX-2-ketone and 4,4-diethyl-5-methylene-DOX-2-ketone.
Carbonic acid methylene ethyl compound can have 1 methylene (compound shown in formula 5) or have 2 methylene.
In addition to the compound shown in formula 3 to formula 5, the cyclic carbonate with unsaturated carbon bond can also is that have phenyl ring
Catechol carbonic ester etc..
It addition, solvent preferably comprises sultone (cyclic sulfonic acid ester), this is because improve the change of electrolyte the most further
Learn stability.As sultone, such as, citation is propane sultone, propene sultone etc..Can be used alone such sulphur
Lactone, or can be therein multiple by being used in mixed way.The content of sultone for example, 0.5 weight %-5 weight % in solvent
(including two end values).
It addition, solvent is preferably containing anhydride, because improving the chemical stability of electrolyte the most further.The example bag of anhydride
Include carboxylic acid anhydrides, disulfonic acid acid anhydride and carboxylic acid and the anhydride of sulfonic acid.The example of carboxylic acid anhydrides includes succinic anhydride, glutaric anhydride and Malaysia
Acid anhydride.The example of disulfonic acid acid anhydride includes ethane disulfonic acid acid anhydride and propanedisulfonic acid acid anhydride.The example bag of the anhydride of carboxylic acid and sulfonic acid
Include sulfosalicylic acid acid anhydride, Sulfo propionic acid acid anhydride and sulfo group butyryl oxide..Can be used alone described anhydride, or can be made by mixing
With therein multiple.The content of anhydride for example, 0.5 weight %-5 weight % (including two end values) in solvent.
Electrolytic salt contains such as-kind or multiple light metal salt such as lithium salts.Can electrolyte the most described below
Salt.
The example of lithium salts includes following.That is, its example includes lithium hexafluoro phosphate, LiBF4, lithium perchlorate and hexafluoro
Arsenic acid lithium.It addition, its example includes tetraphenylboronic acid lithium (LiB (C6H5)4), Loprazolam lithium (LiCH3SO3), fluoroform sulphur
Acid lithium (LiCF3SO3) and tetrachloro-lithium aluminate (LiAlCl4).Its other example includes hexafluorosilicic acid two lithium (Li2SiF6), chlorination
Lithium (LiCl) and lithium bromide (LiBr).
Especially, more preferably at least one in lithium hexafluoro phosphate, LiBF4, lithium perchlorate and hexafluoroarsenate lithium,
And more preferably lithium hexafluoro phosphate, this is because reduce internal resistance, and is derived from higher effect.
Especially, electrolytic salt preferably comprises at least one shown in formula 6 to formula 8 in compound, this is because thus
Obtain higher effect.R31 and R33 in formula 6 can be identical or different.This be equally applicable to the R41 to R43 in formula 7 and
R51 and R52 in formula 8.
Formula 6
In the formula, 1 race's element during X31 is long formula periodic chart or 2 race's element or aluminum.M31 be transition metal,
13 race's elements, 14 race's elements or 15 race's elements in long formula periodic chart.R31 is halogen.Y31 is-(O=) C-R32-C (=
O)-,-(O=) C-C (R33)2-or-(O=) C-C (=O)-.R32 is alkylidene, halogeno alkylen, arlydene or halo Asia virtue
Base.R33 is alkyl, haloalkyl, aryl or halogenated aryl.A3 is one in integer 1-4.B3 is 0,2 or 4.c3、d3、m3
It it is one in integer 1-3 with n3.
Formula 7
In the formula, 1 race's element during X41 is long formula periodic chart or 2 race's elements.M41 is transition metal, long formula week
13 race's elements, 14 race's elements or 15 race's elements in phase table.Y41 is-(O=) C-(C (R41)2)b4-C (=O)-,-(R43)2C-
(C(R42)2)c4-C (=O)-,-(R43)2C-(C(R42)2)c4-C(R43)2-、-(R43)2C-(C(R42)2)c4-S (=O)2-、-
(O=)2S-(C(R42)2)d4-S (=O)2-or-(O=) C-(C (R42)2)d4-S (=O)2-.R41 and R43 is hydrogen, alkyl, halogen
Element or haloalkyl.At least one in R41 and R43 is halogen or haloalkyl respectively.R42 is hydrogen, alkyl, halogen or halo
Alkyl.A 4, e4 and n4 are the integers of 1 or 2.B4 and d4 is one in integer 1-4.C4 is one in integer 0-4.F4 and
M4 is one in integer 1-3.
Formula 8
In the formula, 1 race's element during X51 is long formula periodic chart or 2 race's elements.M51 is transition metal, long formula week
13 race's elements, 14 race's elements or 15 race's elements in phase table.Rf be carbon number be 1-10 (including two end values) fluorinated alkyl or
Carbon number is the fluoro aryl of 1-10 (including two end values).Y51 is-(O=) C-(C (R 51)2)d5-C (=O)-,-(R52)2C-
(C(R51)2)d5-C (=O)-,-(R52)2C-(C(R51)2)d5-C(R52)2-、-(R52)2C-(C(R51)2)d5-S (=O)2-、-
(O=)2S-(C(R51)2)e5-S (=O)2-or-(O=) C-(C (R51)2)e5-S (=O)2-.R51 is hydrogen, alkyl, halogen or halogen
Substituted alkyl.R52 is hydrogen, alkyl, halogen or haloalkyl, and at least one in them is halogen or haloalkyl.a5、f5
It is 1 or 2 with n5.B5, c5 and e5 are one in integer 1-4.D5 is one in integer 0-4.G5 and m5 is in integer 1-3
One.
1 race's element representation hydrogen, lithium, sodium, potassium, rubidium, caesium and francium.2 race's element representation berylliums, magnesium, calcium, strontium, barium and radium.13 units of race
Element represents boron, aluminum, gallium, indium and thallium.14 race's element representation carbon, silicon, germanium, stannum and lead.15 race's element representation nitrogen, phosphorus, arsenic, antimony and
Bismuth.
The example of compound shown in formula 6 includes that formula 6-1 is to the compound shown in formula 6-6.Compound shown in formula 7
Example includes that formula 7-1 is to the compound shown in formula 7-8.Shown in formula 8, the example of compound includes the chemical combination shown in formula 8-1
Thing.Self-evident, compound is not limited to aforesaid compound, and this compound can be other compound, so long as chemical combination
Thing has the structure shown in formula 6 to formula 8.
Formula 6-1 to 6-6
Formula 7-1 to 7-8
Formula 8-1
It addition, electrolytic salt can be with at least one in compound shown in contained 9 to formula 11.Because being derived from relatively
High effect.M and n in formula 9 can be identical or different.This is equally applicable to p, q and the r in formula 11.
Formula 9
LiN(CmF2m+1SO2)(CnF2n+1SO2)…(9)
In the formula, m and n is the integer of 1 or bigger.
Formula 10
In the formula, R61 be carbon number be the perfluorinated alkylidene of the straight chain/side chain of 2-4 (including two end values).
Formula 11
LiC(CpF2p+1SO2)(CqF2q+1SO2)(CrF2r+1SO2)…(11)
In the formula, p, q and r are the integers of 1 or bigger.
Chain imide compound shown in formula 9 includes following compound.That is, its example includes double (fluoroform sulphur
Acyl group) imine lithium (LiN (CF3SO2)2) and double (pentafluoroethane sulfonyl) imine lithium (LiN (C2F5SO2)2).It addition, its example
Including (trifluoromethane sulfonyl group) (pentafluoroethane sulfonyl) imine lithium (LiN (CF3SO2)(C2F5SO2)).It addition, its example bag
Include (trifluoromethane sulfonyl group) (heptafluoro-propane sulfonyl) imine lithium (LiN (CF3SO2)(C3F7SO2)).It addition, its example includes
(trifluoromethane sulfonyl group) (nine fluorine butane sulfonyls) imine lithium (LiN (CF3SO2)(C4F9SO2)).Can be used alone in them
One, or can be multiple by be used in mixed way in them.
The example of the cyclic imide compound shown in formula 10 is the compound shown in facial 10-1 to 10-4 under including.
Can be used alone one therein, or can be therein multiple by being used in mixed way.
Formula 10-1 to 10-4
The example of chain methide (methyde) compound shown in formula 11 includes three (trifluoromethane sulfonyl group) first
Base lithium (LiC (CF3SO2)3)。
Electrolytic salt is preferably 0.3mol/kg-3.0mol/kg (including two end values) relative to the content of solvent, and this is
Because being derived from high ionic conductivity.
The work of secondary cell
In this secondary cell, when charging, such as, lithium ion is deviate from from negative electrode 21, and is contained in spacer body via leaching
Electrolyte in 23 is embedded in anode 22.Meanwhile, when electric discharge, such as, lithium ion is deviate from from anode 22, and contains via leaching
Electrolyte in spacer body 23 is embedded in negative electrode 21.
The method manufacturing secondary cell
Such as, secondary cell is manufactured by following operation.
First, negative electrode 21 is formed.First, active material of cathode, cathode adhesive and negative electrode conductive agent are mixed
To prepare cathode mix, it is dispersed in organic solvent forming pasty state cathode mixture slurry.Subsequently, scraped by use
Cutter, bar coaters etc., be evenly coated with two faces of cathode current collector 21A with this cathode mixture slurry, be dried from
And form cathode active material 21B.Finally, by using roll squeezer etc. that cathode active material 21B is compressed molding,
Heat the most simultaneously.In this case, can by gains compression forming several times.
Then, anode 22 is formed according to the operation of above-mentioned formation anode.In this case, in the two of anode collector 22A
Define on individual face and comprise the spheroidal particle as multiple anode active material particles and the active material of positive electrode of aspherical particle
Layer 22B.
By following secondary cell for assembling.First, after cell device 20 is contained in battery case 11, by insulation board 12
It is arranged on cell device 20.Subsequently, by welding etc. cathode leg 24 is connected to negative electrode pin 15, and will by welding etc.
Anode tap 25 is connected to battery case 11.Afterwards, by laser welding etc., battery cover 13 is fixed on the opening of battery case 11.
Finally, electrolyte is injected into battery case 11 from hand-hole 19, and leaching is contained in spacer body 23.Thereafter, sealing member is passed through
19A seals hand-hole 19.Thus complete the secondary cell shown in Fig. 7 and Fig. 8.
According to the first secondary cell, anode 22 has the structure being similar to above-mentioned anode.Therefore, at charging and discharging
Time, the physical property of anode active material particles deteriorated little with the working time, and anode collector 22A is almost unchanged
Shape.Therefore, the cycle characteristics of excellence and excellent expansion characteristics will be obtained in that.
Especially, the solvent at electrolyte comprise the linear carbonate with halogen, the cyclic carbonate with halogen, tool
Have in the situation of the cyclic carbonate of unsaturated carbon bond, sultone or anhydride, it is possible to improve cycle characteristics further.
It addition, the electrolytic salt at electrolyte comprises lithium hexafluoro phosphate, LiBF4, lithium perchlorate and hexafluoroarsenate lithium
In at least one;Or in the situation of the compound shown in formula 6 to formula 11, it is possible to improve cycle characteristics further.
2-2. the second secondary cell (column type)
Figure 10 and Figure 11 shows the cross section structure of the second secondary cell.Figure 11 shows the screw winding shown in Figure 10
The amplifier section of electrode body 40.
This secondary cell is such as the lithium rechargeable battery of the first secondary cell aforementioned.This secondary cell is in approximation hollow
Spiral winding electrode 40 and a pair insulation board 32 and 33 is accommodated in the battery case 31 of cylindrical shape.Use such electricity
The battery structure of pond shell 31 is so-called column type.
Battery case 31 is made by being such as similar to the material of battery case 11 in the first secondary cell.One end of battery case 31
Open wide, and the other end of battery case 31 is to close.A pair insulation board 32 and 33 is vertically arranged as by spiral winding electrode 40
Between being clipped in, and it is arranged perpendicularly to the extension of screw winding outer peripheral face.
At the opening of battery case 31, battery cover 34, and provide in the relief valve mechanism 35 and PTC within battery cover 34
(positive temperature coefficient) device 36 is by connecting with packing ring 37 caulked.Processed by this caulked, by airtight for the inside of battery case 31
Seal.Battery cover 34 is made up of the material being such as similar to battery case 31.Relief valve mechanism 35 is electrically connected to by PTC device 36
Battery cover 34.In relief valve mechanism 35, fade to certain level or more making interior pressure due to internal short-circuit, external heat etc.
In big situation, discoid plate 35A inverted arch thus cut off the electrical connection between battery cover 34 and spiral winding electrode 40.In temperature
During rising, PTC device 36 makes resistance increase, thus limits electric current to prevent the abnormal delivery in hot weather by high-current leading raw.Packing ring 37
It is made up of such as insulant.The surface of packing ring 37 scribbles such as Colophonium.
In spiral winding electrode 40, stacking spiral shell together with spacer body 43 between the two by negative electrode 41 and anode 42
Circumvolution around.Such as, centrepin 44 is inserted the center of spiral winding electrode 40.In spiral winding electrode 40, by aluminum etc.
The cathode leg 45 made is connected to negative electrode 41, and the anode tap 46 being made up of nickel etc. is connected to anode 42.Anode tap 45 leads to
Cross and be such as welded to relief valve mechanism 35 and be electrically connected to battery cover 34.Anode tap 46 such as welds, thus electrically connects
To battery case 31.
Negative electrode 41 has the most such structure, and in the structure shown here, cathode active material 41B provides has an opposite
Cathode current collector 41A two faces on.The structure of cathode current collector 41A and cathode active material 41B is analogous respectively to
Cathode current collector 21A and the structure of cathode active material 21B in a kind of secondary cell.
Anode 42 has the most such structure, and in the structure shown here, anode active material layers 42B provides has an opposite
Anode collector 42A two faces on.The structure of anode collector 42A and anode active material layers 42B is analogous respectively to
A kind of secondary cell Anodic collector 22A and the structure of anode active material layers 22B.Anode active material layers 42B comprises work
Spheroidal particle and aspherical particle for multiple anode active material particles.
The structure of spacer body 43 and the composition of electrolyte are analogous respectively to the structure of spacer body 23 in the first secondary cell
Composition with electrolyte.
In this secondary cell, such as, when charging, lithium ion is deviate from from negative electrode 41, and is embedded into sun via electrolyte
In pole 42.Meanwhile, such as, when electric discharge, lithium ion is deviate from from anode 42, and is embedded in negative electrode 41 via electrolyte.
Such as, secondary cell is manufactured by following operation.
First, such as, the operation similar with the operation forming negative electrode 21 and anode 22 in the first secondary cell is used,
Negative electrode 41 is formed by forming cathode active material 41B on the two of cathode current collector 41A faces, and by anode
Form anode active material layers 42B on two faces of collector 42A and form anode 42.Subsequently, by welding etc., negative electrode is drawn
Line 45 is connected to negative electrode 41, and by welding etc., anode tap 46 is connected to anode 42.Subsequently, by negative electrode 41 and anode 42
Stacking screw winding together with spacer body 43 between the two, thus form spiral winding electrode 40.Afterwards, by centrepin
44 centers being inserted into spiral winding electrode 40.Subsequently, spiral winding electrode 40 is clipped in a pair insulation board 32 and 33 it
Between, and be contained in battery case 31.In this case, the end of cathode leg 45 is soldered to relief valve mechanism 35, and will
The end of anode tap 46 is soldered to battery case 31.Subsequently, inject the electrolyte in battery case 31, and leaching is contained in spacer body 43
In.Finally, at the opening of battery case 31, filled by self-contained battery lid 34, relief valve mechanism 35 and PTC with packing ring 37 caulked
Put 36.Thus complete the secondary cell shown in Figure 10 and Figure 11.
According to this second secondary cell, anode 42 has the structure of the anode 22 being similar to the first secondary cell.Cause
This, will be obtained in that the cycle characteristics of excellence and excellent expansion characteristics.Other effect of this secondary cell is similar to the first
Those of secondary cell.
The third secondary cell of 2-3. (lamination membranous type)
Figure 12 shows the exploded perspective structure of the third secondary cell.Figure 13 shows along XIII-shown in Figure 12
The exploded cross-sectional that XIII line is taken.
This secondary cell is such as the lithium rechargeable battery of the first secondary cell aforementioned.In this secondary cell, mainly
Ground, is contained in the spiral winding electrode 50 that cathode leg on it 51 is connected with anode tap 52 in film packaging part 60.Make
It is so-called lamination membranous type with the battery structure of such packaging part 60.
Such as, cathode leg 51 and anode tap 52 are respectively from the inside of packaging part 60 leads in same direction
Portion.But, cathode leg 51 and anode tap 52 are relative to the allocation position of spiral winding electrode 50, their lead direction
Etc. being not particularly limited.Cathode leg 51 is made up of such as aluminum etc., and anode tap 52 is made by such as copper, nickel or rustless steel etc.
Become.These materials are the most lamellar or netted.
Packaging part 60 is made up of laminate film, in this laminate film, such as by fused layers, metal level and sealer with this
Order carries out stacking.In this case, such as, the respective outer edge of the fused layers of two films is by fusion, binding agent etc.
It is bonded to each other so that fused layers and spiral winding electrode 50 are relative to each other.The example of fused layers includes by polyethylene, polypropylene
Etc. the film made.The example of metal level includes aluminium foil.The example of sealer includes by nylon, polyethylene terephthalate
The film that ester etc. are made.
Particularly as packaging part 60, preferably wherein by polyethylene film, aluminium foil and nylon membrane with the aluminum of this order stacking
Laminate film.But, packaging part 60 can be by having the laminate film of other laminate structures, polymeric film such as polypropylene screen or metal
Film replaces above-mentioned aluminum laminated film to make.
The bonding film 61 preventing extraneous air from entering is inserted into packaging part 60 and cathode leg 51, anode tap 52 it
Between.Bonding film 61 is made up of the material relative to cathode leg 51 and anode tap 52 with contact performance.Such material
Example includes, such as vistanex such as polyethylene, polypropylene, modified poly ethylene and modified polypropene.
In spiral winding electrode 50, negative electrode 53 and anode 54 are together with spacer body 55 between the two and electrolyte 56
Stacking screw winding.Its outermost perimembranous 57 is protected by by protecting band.
Negative electrode 53 has the most such structure, and in this structure, cathode active material 53B provides and has an opposite
On two faces of cathode current collector 53A.The structure of cathode current collector 53A and cathode active material 53B is analogous respectively to first
Plant cathode current collector 21A and the structure of cathode active material 21B in secondary cell.
Anode 54 has the most such structure, and in the structure shown here, anode active material layers 54B provides has an opposite
Anode collector 54A two faces on.The structure of anode collector 54A and anode active material layers 54B is analogous respectively to
A kind of secondary cell Anodic collector 22A and the structure of anode active material layers 22B.Anode active material layers 54B has work
Spheroidal particle and aspherical particle for multiple anode active material particles.
Spacer body 55 is similar to that the structure of spacer body 23 in the first secondary cell.
Dielectric substrate 56 is the so-called gel electrolyte containing electrolyte and the polymer keeping electrolyte.Preferably gel
Electrolyte, this is because obtain high ionic conductivity (such as, at room temperature for 1mS/cm or bigger) and be possible to prevent
The liquid leakage of electrolyte.
The example of polymer includes as follows.That is, its example include polyacrylonitrile, Kynoar, politef, poly-six
Fluoropropene, poly(ethylene oxide), poly(propylene oxide), polyphosphazene, polysiloxanes and polyvinyl fluoride.It addition, its example includes poly-acetic acid
Vinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethylacrylic acid, butadiene-styrene rubber, nitrile rubber, polyphenyl
Ethylene and Merlon.It addition, its example includes the copolymer of vinylidene and hexafluoropropene.Can be used alone these polymerizations
One in thing, or can by be used in mixed way therein two or more.In particular it is preferred to Kynoar or partially
Fluorothene and the copolymer of hexafluoropropene, because such polymer is electrochemically stable.
The composition of electrolyte is similar to the composition of electrolyte in the first secondary cell.But, as gel electrolyte
Dielectric substrate 56 in, the solvent in electrolyte represents generalized concept, not only includes liquid flux but also includes dissociating electricity
Solve the solvent with ionic conductivity of matter salt.Therefore, use in the situation of the polymer with ionic conductivity wherein, poly-
Compound is also included within solvent.
Replace the gel electrolyte layer 56 that wherein electrolyte is kept by polymer, can directly use electrolyte.This
In situation, electrolysis immersion is contained in spacer body 55.
In this secondary cell, when charging, such as, lithium ion is deviate from from negative electrode 53, and embedding via dielectric substrate 56
Enter in anode 54.Meanwhile, when electric discharge, such as, lithium ion is deviate from from anode 54, and embeds negative electrode 53 via dielectric substrate 56
In.
For example, it is possible to manufactured the secondary cell including gel electrolyte layer 56 by following three kinds of operations.
In the first manufacture method, first, such as, by similar with negative electrode 21 in the first secondary cell and anode 22
Formation process form negative electrode 53 and anode 54.Especially, alive by forming negative electrode on two faces of cathode current collector 53A
Property material layer 53B and form negative electrode 53, and by two faces of anode collector 54A formed anode active material layers
54B and form anode 54.Subsequently, preparation comprises the precursor solution of electrolyte, polymer and solvent.Coating with this precursor solution
After negative electrode 53 and anode 54, solvent is made to volatilize to form gel electrolyte 56.Subsequently, by welding etc., cathode leg 51 is connected
It is connected to cathode current collector 53A, and by welding etc., anode tap 52 is connected to anode collector 54A.Subsequently, it will thus provide have electricity
Solve the negative electrode 53 of matter layer 56 and anode 54 together with spacer body 55 between the two stacking screw winding to obtain lamilated body.It
After, protection band 57 is adhered to its outermost perimembranous thus forms spiral winding electrode 50.Finally, such as, by screw winding
After electrode body 50 is clipped between the membranaceous packaging part of two panels 60, by the outer edge of the bond package parts 60 such as heat fused, to encapsulate spiral shell
Rotation rolled electrode bodies 50.Now, bonding film 61 is inserted between cathode leg 51, anode tap 52 and packaging part 60.Thus,
Complete the secondary cell shown in Figure 12 and Figure 13.
In the second manufacture method, first, cathode leg 51 is connected to negative electrode 53, and anode tap 52 is connected to
Anode 54.Subsequently, stacking screw winding together with spacer body 55 between the two by negative electrode 53 and anode 54.Afterwards, will protect
Protecting band 57 adheres to its outermost perimembranous, thus forms the screw winding body of the precursor as spiral winding electrode 50.Subsequently, exist
After screw winding body being clipped between the membranaceous packaging part of two panels 60, the outermost perimembranous in addition to side is glued by heat fused etc.
Close to obtain pouch-shaped state, and screw winding body is contained in bag-shaped packaging part 60.Subsequently, preparation is containing electrolyte, work
Electrolyte for monomer, polymerization initiator and other material such as polymerization inhibitor if desired for polymer raw material forms
Material, is injected in bag-shaped packaging part 60.Afterwards, the opening of packaging part 60 is carried out hermetic seal by heat fused etc..
Finally, make monomer thermal polymerization to obtain polymer.Thus, form gel electrolyte layer 56.Therefore, this secondary cell is completed.
In the third manufacture method, in addition to all scribble the spacer body 55 of polymer first by two sides, by with upper
State the identical mode of the second manufacture method form screw winding body and be contained in bag-shaped packaging part 60.As coating point
The example of the polymer of spacer 55, including containing vinylidene as the polymer of component, i.e. homopolymer, copolymer and multi-component copolymer
Thing.Its object lesson includes Kynoar, containing vinylidene and hexafluoropropene as the bipolymer of component, Yi Jihan
There is vinylidene, hexafluoropropene and the CTFE terpolymer as component.As polymer, except above-mentioned containing inclined fluorine
Outside ethylene is as the polymer of component, it is also possible to comprise one or more other polymer.Subsequently, electrolyte is prepared and by it
It is injected in packaging part 60.Afterwards, by the opening of the sealed packages such as heat fused 60.Finally, heat gains, simultaneously will weight
Thing applies to packaging part 60, and is contacted with negative electrode 53 and anode 54 by spacer body 55, and between making polymer be in.Thus,
Will electrolysis immersion containing in polymer, and make Gelation thus form dielectric substrate 56.Therefore, this secondary is completed
Battery.
In the third manufacture method, compared with the first manufacture method, it is suppressed that the expansion of secondary cell.It addition,
In the third manufacture method, compared with the second manufacture method, stay electricity hardly as the monomer of polymer raw material, solvent etc.
Solve in matter layer 56.It addition, the forming step of polymer is advantageously controlled.Therefore, at negative electrode 53/ anode 54/ spacer body 55
And sufficient contact performance can be obtained between dielectric substrate 56.
According to this third secondary cell, anode 54 has the knot of the anode 22 being similar to that the first secondary cell
Structure.Therefore, it is possible to obtain excellent cycle characteristics and excellent expansion characteristics.Other effect of this secondary cell is similar to first
Plant those effects of secondary cell.