CN102496712A - Fabrication method for lithium battery anode material - Google Patents
Fabrication method for lithium battery anode material Download PDFInfo
- Publication number
- CN102496712A CN102496712A CN2011104154503A CN201110415450A CN102496712A CN 102496712 A CN102496712 A CN 102496712A CN 2011104154503 A CN2011104154503 A CN 2011104154503A CN 201110415450 A CN201110415450 A CN 201110415450A CN 102496712 A CN102496712 A CN 102496712A
- Authority
- CN
- China
- Prior art keywords
- lithium
- predecessor
- slurry
- anode material
- lithium battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a fabrication method for a lithium battery anode material, which includes the steps of providing one of a lithium-ion precursor, a phosphate precursor and an iron ion precursor to be mixed with powder including a plurality of porous nano particles; mixing mixed powder with water to form first slurry; granulating and roasting the first slurry to form a first spherical precursor; mixing the first spherical precursor, a conductive material and water to form second slurry; granulating and roasting the second slurry to form a plurality of porous lithium oxide micron grains; and mixing the porous lithium oxide micron grains, a conductive carbon material and binder to form the lithium battery anode material.
Description
The application is the application number submitted on January 28th, 2008 the dividing an application for the application for a patent for invention of " anode material of lithium battery, its manufacturing approach and use the lithium secondary battery of this material " that be 200810006703.x and denomination of invention.
Technical field
The present invention relates to a kind of electrode material, and particularly relates to a kind of manufacturing approach of anode material of lithium battery.
Background technology
Lithium battery is a kind of of secondary cell (getting final product TunePower), and it is mainly formed by positive pole, liquid state organic electrolyte or the solid electrolyte of lithium alloy oxide and as the carbon material of negative pole.The application of lithium battery at present mainly is like 3C articles for use such as mobile phone, notebook computer, digital camera, video cameras, with the power supply source as the required high-energy-density of the above-mentioned 3C Product of supply.
Yet; Has more high-power application for more above-mentioned 3C articles for use; For example be application such as electric motor car and hand tool; The application of lithium secondary battery is prematurity still then, and its reason is that the anode electrode material of applied lithium metal oxide in the present lithium secondary battery has the low excessively problem of electrical conductivity, so when high discharging current, will meet with the not enough problem of material internal current potential; Thereby make the usability that has reduced material when the embedding/embedding of lithium ion goes out in the lithium secondary battery, and then deterioration lithium battery high electric current charging and discharging capabilities with and cycle life.
Therefore, the positive electrode that just needs a kind of electrical conductivity more to promote with the life-span and the charging and discharging capabilities of lifting lithium secondary battery, and then improves its application in the high power aspect.
Summary of the invention
The positive electrode that the object of the present invention is to provide a kind of electrical conductivity more to promote with the life-span and the charging and discharging capabilities of lifting lithium secondary battery, and then improves its application in the high power aspect.
Therefore, the invention provides the manufacturing approach of a kind of anode material of lithium battery, anode material of lithium battery and use the lithium secondary battery of above-mentioned anode material of lithium battery.
According to an embodiment, the invention provides a kind of anode material of lithium battery, comprising:
One porousness lithium oxide micro particles, wherein this porousness lithium oxide micro particles comprises: a plurality of porousness lithium oxide nano-particles are provided with one first conductive layer in these porousness lithium oxide nano-particles; One hole is limited and forms in linking back institute these porousness lithium oxide nano-particles; One second conductive layer is coated on the surface of one of these porousness lithium oxide nano-particles at least and contacts this first conductive layer, in said porousness lithium oxide micro particles, to form the 3-D conductive network; And a conductive fiber, link said second conductive layer.Have a plurality of nanometer lithium oxide particles, nanoporous passage and nanometer 3-D conductive network in this porousness lithium oxide micro particles and form, have a conductive fiber outward and connect into outer second conductive layer.
According to an embodiment, the invention provides a kind of lithium secondary battery, comprising:
One positive pole comprises aforesaid anode material of lithium battery; One negative pole; And an ionic conduction layer, be folded between said positive pole and the said negative pole.
According to an embodiment, the invention provides a kind of manufacturing approach of two stages of anode material of lithium battery calcining, comprising:
Provide to comprise one of lithium ion predecessor, phosphate predecessor and iron ion predecessor mixed-powder, wherein this mixed-powder comprises a plurality of porousness nano particles; Mix this mixed-powder and water to form one first slurry; This first slurry of granulation calcination is to form the spherical predecessor of a first kind; Mix the spherical predecessor of this first kind, electric conducting material and water to form one second slurry; This second slurry of granulation calcination is to form a plurality of porousness lithium oxide micro particles; And mix these porousness lithium oxide micro particles, a conductive carbon material and a binding agent, to form this anode material of lithium battery.
The present invention is through using iron lithium phosphate through upgrading as positive electrode; It has more surface area, less pore size, lower resistance value and suitable electric conducting material and covers situation, thus help promoting the iron lithium phosphate structure electron conduction, improve the evolving path of lithium ion and be prone to make make when being added with electrolyte solution and be full of hole and increase response area and reaction chance in order to ionic conduction and through increasing surface area.
Use in the lithium secondary battery of positive electrode of the present invention; Because the porous crack conductive structure that porousness lithium metal oxide micro particles is construed as in the structure of positive electrode; Thereby has a splendid electrical performance; Be beneficial to high current discharge, also promptly be beneficial to high-power application, and be applicable to the application that discharges and recharges of high power value; Thereby show that the iron lithium phosphate positive electrode through upgrading has the good conductive degree among the present invention, and then can derive electronics more easily and make lithium ion be prone to break away from the iron lithium phosphate crystal.
In order to let above and other objects of the present invention, characteristic and the advantage can be more obviously understandable, hereinafter is special lifts a preferred embodiment, and conjunction with figs., elaborates as follows:
Description of drawings
Fig. 1 is a sketch map, has shown the section situation according to the cathode plate for lithium secondary battery structure of one embodiment of the invention;
Fig. 2 is a sketch map, has shown the structure according to the positive electrode of one embodiment of the invention;
Fig. 3 is a sketch map, has shown among Fig. 2 the structure of contained conducting particles in the positive electrode;
Fig. 4 a, 4b and 4c are a series of sketch mapes, have shown the crystal structure according to positive electrode in one embodiment of the invention respectively;
Fig. 5 is a sketch map, has shown the lithium secondary battery according to one embodiment of the invention;
Fig. 6 is a sketch map, has shown the lithium secondary battery according to another embodiment of the present invention;
Fig. 7 is a chart, has shown the X light diffracting analysis result according to the positive electrode of one embodiment of the invention;
Fig. 8 is a chart, has shown the electrochemical analysis result according to the positive electrode of one embodiment of the invention;
Fig. 9 is a chart, has shown the electrochemical analysis result according to the positive electrode of one embodiment of the invention; And
Figure 10 is a chart, has shown the electrochemical analysis result according to the positive electrode of the present invention's one comparative example.
Wherein, primary clustering symbol description:
10~collector plate;
12~positive electrode material layer;
14~anode plate structure;
16~lithium metal oxide;
17~conductive carbon material;
18~binding agent;
20~porousness lithium oxide micro particles;
30~be coated with the porousness lithium oxide nano-particles of conductive layer;
30 '~be not coated with the porousness lithium oxide nano-particles of conductive layer;
32~conductive layer;
34~hole;
36~conductive fiber;
40~conductive layer;
50~nanocrystal;
100~column type lithium secondary battery;
102~ionic conduction layer;
104~positive pole;
106~negative pole;
108~shell;
110~positive terminal;
112~negative terminal;
200~coin type lithium secondary battery;
202~ionic conduction layer;
204~positive pole;
206~anode cover;
208~negative pole;
210~negative electrode casing;
250~gasket.
Embodiment
Please, shown section situation according to the anode plate structure 14 of one embodiment of the invention with reference to the sketch map of Fig. 1.At this, anode plate structure 14 has comprised the positive electrode material layer of coating on the collector plate 10 12.Collector plate for example is the conductive sheet metal of aluminium (Al), aluminium/carbon (Al/C), nano aluminum/aluminium materials such as (nano-Al/Al).In positive electrode rete 12, mainly comprised lithium metal oxide 16, conductive carbon material 17 and binding agent (binder) 18, wherein lithium metal oxide 16: conductive carbon material 17: the weight ratio of binding agent 18 is approximately between 93: 3: 4~75: 10: 15.
Please with reference to the sketch map of Fig. 2; The signal situation that has shown porousness lithium oxide micro particles 20 contained in the lithium metal oxide 16 according to one embodiment of the invention; And lithium alloy oxide 16 mainly is to form (not showing that at this it combines situation) by 20 granulations of a plurality of porousness lithium oxide micro particles, and its contained positive electrode particle 20 has respectively between 5 microns~20 microns average grain diameter, between 1m
2/ g~50m
2The surface area of/g and between the porosity of 0.02c.c./g~0.12c.c./g.
As shown in Figure 2; The schematic construction that has only shown a porousness lithium oxide micro particles 20 separately; It comprises a plurality of porousness lithium oxide nano-particles 30, and these porousness lithium oxide nano-particles 30 have the average grain diameter between 100 nanometers~500 nanometers respectively.
These porousness lithium oxide nano-particles 30 therebetween then limit after linking and form a plurality of holes 34; And above-mentioned hole 34 can be orderly or unordered misclosure hole and have between one of 10~30 nanometers size; In lithium secondary battery is used, electrolyte or moistening position and the electrochemical response area of electrolyte being provided, and then raising ionic conduction speed.
In addition, on the surface of most porousness lithium oxide nano-particles 30, be coated with a conductive layer 32.Yet, in porousness lithium oxide micro particles 20, still have the porousness lithium oxide nano-particles that is not coated on a small quantity for conductive layer 32, be denoted as 30 ' at this.In addition; In porousness lithium oxide micro particles 20, also include several conductive fibers 36; It is to be linked to conductive layer 32 and possibly to protrude in the surface of porousness lithium oxide micro particles 20 and/or extend in the hole 34 between porousness lithium oxide nano-particles 30/30 ', is positioned at the inner porousness lithium oxide nano-particles 30/30 ' of porousness lithium oxide micro particles 20 so that link.The material of conductive layer 32 for example is metal, conduction organic material or conducting inorganic material materials such as (like conductive carbon), and has one of 3~10 nanometers thickness.And the material of conductive fiber 36 for example is metal, conduction organic material or conducting inorganic material materials such as (like conductive carbon), and its average diameter is about 0.5~3 micron.So, the formation through conductive layer 32 and conductive fiber 36 with possibly link situation, thereby can in lithium oxide micro particles 20, be construed as three-dimensional (3-D) conductive network and help the conduction of electronics.
Please with reference to the signal situation of Fig. 3, it has shown among Fig. 2 the structure of contained porousness lithium oxide nano-particles in the porousness lithium oxide micro particles 20.As shown in Figure 3; Be coated with a conductive layer 32 on the surface of this porousness lithium oxide nano-particles 30; This porousness lithium oxide nano-particles 30 has a plurality of hole (not shown)s; Its 50 of nanocrystal by a plurality of lithium metal oxides is formed, and between these nanocrystals 50, then is formed with a conductive layer 40, and 40 contacts of conductive layer also link conductive layer 32.At this, 50 the average grain diameters of nanocrystal in the porousness lithium oxide nano-particles 30 with 10~100 nanometers.So, through formation and the binding of conductive layer 40, thereby can in lithium oxide nano-particles 30, be construed as the conduction that three-dimensional (3-D) conductive network is beneficial to electronics with conductive layer 32.
At this, the nanocrystal 50 of lithium metal oxide powder can comprise the lithium metal oxide of layer structure, spinel structure and olivine structural.Material with nanocrystal 50 of layer structure for example is LiCoO
2, LiNiO
2, LiMnO
2Or LiCo
xNi
yMn
zO
2(wherein x+y+z=1), Fig. 4 a has then illustrated the LiCoO that adopts
2The signal situation of the layer structure of material nano crystal.Material with nanocrystal 50 of spinel structure then for example is Li
2Ti
5O
8Or LiMn
2O
4, Fig. 4 b has then illustrated the LiMnO that adopts
2The signal situation of the spinel structure of material nano crystal.50 of nanocrystals with olivine structural for example are LiFePO
4/ C, LiFePO
4Or Li
xM
1-(d+t+q+r)D
dT
tQ
qR
r(XO
4), wherein M is the mixture of selecting from Fe, Mn, Co, Ti, Ni or above-mentioned material, and D is element M g, Ni, Co, Zn, Cu and the Ti that selects from divalence; And T is element al, Ti, Cr, Fe, Mn, Ga, Zn and the V that selects from trivalent, and Q is element ti, Ge, Sn and the V that selects from tetravalence, and R is element V, Nb and the Ta that selects from pentavalent; And X is the mixture of selecting from Si, S, P, V or above-mentioned material, wherein 0≤x≤1,0≤d, t; Q, r≤1 and one of d, t, q and r are non-vanishing at least.Fig. 4 c has then illustrated employing LiFePO
4The signal situation of olivine structural.
Fig. 5 is a sketch map; Shown lithium secondary battery 100 according to one embodiment of the invention; Negative pole (anode) 106 and anodal (cathode) 104 that it has the column profile and is oppositely arranged, and negative pole 106 and anodal 104 is to intercept mutually for 102 on ionic conduction layer (ionic conductor).At this; Negative pole 106, positive pole 104 are to be 108 coatings of shell (housing) with ionic conduction layer 102, and negative pole 106 and anodal 104 then is linked to a negative terminal (anode terminal) 112 and one positive terminal (cathodeterminal) 110 respectively.In lithium secondary battery as shown in Figure 5; Anodal 104 is to adopt positive electrode material layer 12 as shown in Figure 1; Negative pole 106 then for example is carbon, graphite, carbonaceous mesophase spherules (mesocarbonmicrobeads; MCMB) or the substrate of lithium conductive material such as (Li), then include the barrier film or the gelated electrolyte that contain lithium electrolyte in the ionic conduction layer 102.At this, through adopting positive electrode material layer 12 of the present invention, lithium secondary battery 100 thereby be applicable to and need to use the product of high charge-discharge power to use.
Fig. 6 then is a sketch map; It has shown the lithium secondary battery 200 according to another embodiment of the present invention; It has a coin shape external form (coin shape); It has positive pole 204 that comprises the positive electrode rete and the negative pole 208 that comprises the negative material rete, and wherein negative pole 208 is storehouses and is arranged at anodal 204 top and between negative pole 208 and anodal 204, is gripped with ionic conduction layer 202.At this, negative pole 210, ionic conduction layer 202 with coated by anode cover 206 and be 210 coatings of negative electrode casing in side of the positive electrode through back anodal 204 one on top of another in negative side, anode cover 206 and negative electrode casing 210 are then respectively as negative terminal and positive terminal.At this, in one of anode cover 206 portion, then be embedded with gasket (gasket) 250, so as to avoiding the outflow of lithium secondary battery 200 contained materials.
In lithium secondary battery as shown in Figure 6; Anodal 204 is to adopt positive electrode material layer 12 as shown in Figure 1; Negative pole 208 then for example is carbon, graphite, carbonaceous mesophase spherules (mesocarbon microbeads; MCMB) or the substrate of lithium conductive material such as (Li), then include the barrier film or the gelated electrolyte that contain lithium electrolyte in the ionic conduction layer 202.At this, through adopting positive electrode material layer 12 of the present invention, thereby be applicable to and need to use the product of high charge-discharge power to use.
In addition, the present invention also provides a kind of manufacturing approach of positive electrode, comprises the following steps:
(a) powder of a lithium ion predecessor is provided, it comprises LiOH, Li
2CO
3Or C
2H
5COOLi; The powder of monophosphate predecessor, it comprises (NH
4)
2HPO
4, NH
4H
2PO
4, H
3PO
4Or (NH
4)
3PO
4And the powder of an iron ion predecessor, it comprises Fe
2C
2O
4XH
2O, Fe, Fe
2(C
2O
4)
3Or Fe (C
2H
5COO)
2, the powder of above-mentioned predecessor comprises a plurality of porousness nano particles;
(b) powder of the above-mentioned three kinds of predecessors of mixing and water are to form one first slurry, and the mixed proportion of the powder of wherein above-mentioned three kinds of predecessors is then approximately between 1: 1: 1 (mole ratio);
(c) above-mentioned first slurry of granulation calcination is to form spherical (sphere-like) predecessor of a first kind;
(d) mix the spherical predecessor of the above-mentioned first kind, electric conducting material and water to form one second slurry;
(e) above-mentioned second slurry of granulation calcination is to form a plurality of porousness lithium oxide micro particles; And
(f) mix these porousness lithium oxide micro particles, a conductive powder, a binding agent, be applicable to the anode plate of lithium battery with formation.
In above-mentioned enforcement situation; In step (b) in formed first slurry ratio of predecessor powder and water between 20: 80~60: 40 (wt%); And in step (d) in formed second slurry ratio of the spherical predecessor of the first kind, electric conducting material and water between 46: 4: 50~40: 10: 50 (wt%); The mixed proportion of porousness lithium oxide micro particles, conductive powder and binding agent in step (f) is then approximately between 93: 3: 4~75: 10: 15 (wt%); And after mixing, it is coated on (for example being aluminium foil) on the collecting board in above-mentioned material, to form the cathode plate for lithium secondary battery pole plate.
In addition, in above-mentioned enforcement situation, employed electric conducting material is metal, conduction organic material or conducting inorganic material materials such as (like conductive carbon) in the step (d), for example is conductive carbon powder or metal dust.
Moreover in the foregoing description, the granulation calcination program of step (c) for example is the single program of spraying thermal decomposition program or is a recombination process that comprises spray drying program and sintering program.The execution temperature of the granulation calcination program in step (c) is under 200~400 ℃, carrying out, and the execution temperature of the granulation calcination program in the step (e) is then under 600~850 ℃, carrying out.
[embodiment]
At first, the predecessor mixed-powder of 750 grams and the water of 750 grams are mixed to form one first slurry.Then via a granulation calcination program with this first slurry to form the spherical predecessor of pulverous first kind.For example add the composite steps program of sintering for the one step program of employing spraying thermal decomposition program or for employing spray drying program in this granulation calcination program.Above-mentioned granulation section burning program is under 250 ℃ temperature, carrying out.
Then; 100 these first ball-type predecessors of gram and 6 gram electric conducting materials and 100 are restrained after the solvent forming one second slurry, and above-mentioned second slurry of granulation calcination comprises the iron lithium phosphate positive electrode of a plurality of porousness micro particles with formation under 600~850 ℃ temperature.At this, the iron lithium phosphate positive electrode is made up of similar porousness micro particles shown in Figure 1, and electric conducting material is to use conductive carbon.
With above-mentioned iron lithium phosphate positive electrode and conductive carbon material and polyvinylidene fluoride (polyvinylidene; PVDF) after 84: 7: 9 ratio of foundation is weighed; Adding N-N-methyl 2-pyrrolidone N-(NMP) subsequently is slurry to be uniformly mixed into; Utilizing 120 microns scraper that slurry is coated thickness is on 20 microns the aluminium foil and in through carrying out vacuum bakeout behind the heating, drying removing nmp solvent, and then forms an anode plate.
Then roll above-mentioned electrode pad and it formation diameter is about 12 centimetres coin type pole plate, and employing lithium metal is the LiPF that contains of 1M as negative pole, above-mentioned coin type pole plate as anodal and employing concentration
6, propene carbonate (PC), ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio is 3: 5: 2) solution is as electrolyte solution, and then accomplishes the making of coin type battery.
[comparative example]
In this comparative example, employed iron lithium phosphate positive electrode is identical with processing step and embodiment.Yet, in comparative example, only use the iron lithium phosphate positive electrode and do not add electric conducting material is arranged (so can not be formed with the 3-D conductive network), and then prepare the relatively iron lithium phosphate positive electrode of usefulness.
In this comparative example, employed lithium oxide material and technology step is identical with embodiment.Yet in comparative example, only using the iron lithium phosphate material and not adding has electric conducting material, and then prepares the relatively coin type battery of usefulness.
Please, shown the X light diffracting analysis result of embodiment and comparative example respectively with reference to chart shown of Fig. 7 X light diffracting analysis result according to the positive electrode of one embodiment of the invention.As shown in Figure 7; Embodiment has similar X light diffracting analysis result and the difference on the intensity is only arranged with comparative example; Therefore confirmed that the interior iron lithium phosphate structure of embodiment and comparative example is still possessed the characteristic of olivine structural and behind the process program upgrading of embodiment, the crystalline phase in its structure can't be changed.
In addition, please with reference to the physical characteristic analysis result of the iron lithium phosphate shown in the following table 1, shown the physical characteristic of iron lithium phosphate in embodiment and the comparative example respectively.
The real density of the iron lithium phosphate in comparative example (true density) is about 3.59g/c.c., and powder density (tap density) then is about 0.65g/c.c, and then recording carbon content through elementary analysis is 0, does not have the surface that carbon is covered in iron lithium phosphate.Adopt its resistance of four-point probe test then can't measure in addition, this demonstration be its literature value (please with reference to Solid State Ionics 176 (2005) 1801), briquetting resistance is 10
9Ω, and pole plate resistance is 1.57m Ω.The surface area of measuring its every gram through specific area (BET) method in addition is 14.61m
2/ g is that the hole of 2.06 nanometers and every gram is 0.03c.c./g and measure pore size through pore-size distribution (BJH) rule.
The real density of the iron lithium phosphate in embodiment (true density) is about 3.31g/c.c., and powder density (tap density) then is about 0.79g/c.c, and then recording carbon content through elementary analysis is 2~3%, has the surface that carbon is covered in iron lithium phosphate.Adopting its resistance of four-point probe test in addition is 0.67k Ω, and pole plate resistance is 0.67m Ω.The surface area of measuring its every gram through specific area (BET) method in addition is 30.3m
2/ g is that the aperture of 2.06 nanometers and every gram is 0.06c.c./g and measure pore size through pore-size distribution (BJH) rule.
Comparison through above-mentioned physical characteristic; Can learn among the embodiment that iron lithium phosphate through upgrading has more surface area, less pore size, lower resistance value and suitable electric conducting material and covers situation, thus help promoting iron lithium phosphate structure among the embodiment electron conduction, improve the evolving path of lithium ion and be prone to make make when being added with electrolyte solution and be full of hole and increase response area and reaction chance in order to ionic conduction and through increasing surface area.
Table 1: the physical characteristic of iron lithium phosphate
Please, then shown electrochemical analysis result, shown the charging and discharging curve figure of lithium secondary battery among the embodiment according to the positive electrode of the present invention's one comparative example with reference to the chart of Fig. 8.As shown in Figure 8; After earlier lithium secondary battery being discharged and recharged through 0.1C, 0.2C, 1C, 2C, 3C, 5C, 8C and 12C; At first after discharging and recharging 50 circulations of life test under the condition of 0.2C/0.2C (charge/discharge), can find that capacitance is to be maintained at about 140mAh/g.Then lithium secondary battery is discharged and recharged 50 circulations of life test under the condition of 0.5C/1C (charge/discharge), can find that capacitance can be maintained at about 132mAh/g.Then again lithium secondary battery is discharged and recharged 50 circulations of life test under the condition of 1C/3C (charge/discharge), can find that capacitance can be maintained at about 121mAh/g.Therefore, because the porous crack conductive structure that porousness lithium metal oxide micro particles is construed as in the structure of the positive electrode in the lithium secondary battery, thereby have splendid electrical performance.
Fig. 9 and Figure 10 then are a series of charts, have shown the electrochemical analysis result according to the positive electrode of one embodiment of the invention respectively, have shown the charging and discharging curve figure of embodiment and comparative example respectively.
In Fig. 9; The lithium secondary battery of embodiment is carried out discharging and recharging the first time with the speed of 0.1C, and its capacitance is 152/141 (charge/discharge) mAh/g, has the irreversible amount (about 7.3% loss) of 11mAh/g; And its capacitance only is left 132mAh/g when 0.2C discharges; Reduce 9mAh/g during only than the discharge rate of 0.1C, even capacitance also has 100mAh/g during to the discharge rate of 3C, and even during to the discharge rate of 12C capacitance also have 80mAh/g.
And in Figure 10; Lithium secondary battery in the comparative example carries out discharging and recharging the first time with the speed of 0.1C; Its capacitance is 155/141 (charge/discharge) mAh/g; Irreversible amount (about 9% loss) with 14mAh/g, and when following of the speed of 0.2C is discharged the only remaining 118mAh/g of its capacitance, and its capacitance only is left 17mAh/g when discharging under the speed when 1C.
Result with reference to Fig. 9 and Figure 10 compares; Be appreciated that the iron lithium phosphate positive electrode before the electrochemical analysis result (please with reference to Figure 10) who adopts the lithium secondary battery (comparative example) of made iron lithium phosphate positive electrode without method of the present invention demonstrates upgrading not is unfavorable for high current discharge, also promptly is unfavorable for high-power application.In addition; The electrochemical analysis result who then demonstrates the iron lithium phosphate positive electrode behind upgrading in the electrochemical analysis result's (please with reference to Fig. 9) of the lithium secondary battery (embodiment) that adopts the made iron lithium phosphate positive electrode of method of the present invention electrochemical analysis result (please with reference to Figure 10) all is superior to for containing the not performance of the lithium secondary battery of upgrading iron lithium phosphate positive electrode; And be applicable to the application that discharges and recharges of high power value; Thereby show that the iron lithium phosphate positive electrode through upgrading has the good conductive degree among the present invention, and then can derive electronics more easily and make lithium ion be prone to break away from the iron lithium phosphate crystal.In addition, owing to be porous material, so also have high surface area, make lithium ion embed the chance raising that embedding goes out, thereby be beneficial to the carrying out of high current discharge through the iron lithium phosphate material of upgrading.
Though the present invention with preferred embodiment openly as above; Right its is not in order to limit the present invention; Any those skilled in the art; Do not breaking away from the spirit and scope of the present invention, when can doing various changes and retouching, so protection scope of the present invention is as the criterion when looking the accompanying Claim book person of defining.
Claims (7)
1. the manufacturing approach of an anode material of lithium battery comprises:
Provide to comprise one of lithium ion predecessor, phosphate predecessor and iron ion predecessor mixed-powder, wherein said mixed-powder comprises a plurality of porousness nano particles;
Mix said mixed-powder and water to form one first slurry;
Said first slurry of granulation calcination is to form the spherical predecessor of a first kind;
Mix the spherical predecessor of the said first kind, electric conducting material and water to form one second slurry;
Said second slurry of granulation calcination is to form a plurality of porousness lithium oxide micro particles; And
Mix these porousness lithium oxide micro particles, a conductive carbon material and a binding agent, to form this anode material of lithium battery.
2. the manufacturing approach of anode material of lithium battery according to claim 1, the said mixed-powder in wherein said first slurry and the ratio of water are 20: 80~60: 40 (wt%).
3. the manufacturing approach of anode material of lithium battery according to claim 1, the ratio of the spherical predecessor of the said first kind in wherein said second slurry, this conductive carbon powder and water is 46: 4: 50~40: 10: 50 (wt%).
4. the manufacturing approach of anode material of lithium battery according to claim 1, the ratio of the said porousness lithium oxide micro particles in the wherein said anode material of lithium battery, said conductive carbon material and said binding agent is 93: 3: 4~75: 10: 15 (wt%).
5. the manufacturing approach of anode material of lithium battery according to claim 1, wherein said conductive powder is conductive carbon powder or metal dust.
6. the manufacturing approach of anode material of lithium battery according to claim 1, the granulation calcination program that wherein forms the said first ball-type predecessor is spraying thermal decomposition program.
7. the manufacturing approach of anode material of lithium battery according to claim 1, the said lithium ion predecessor in the wherein said mixed-powder is to select free LiOH, Li
2CO
3And C
2H
5One of cohort that COOLi forms, said phosphate predecessor is to select freedom (NH
4)
2HPO
4, NH
4H
2PO
4, H
3PO
4And (NH
4)
3PO
4Form one of cohort, and this iron ion predecessor is to select free Fe
2C
2O
4XH
2O, Fe, Fe
2(C
2O
4)
3And Fe (C
2H
5COO)
2Form one of cohort.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011104154503A CN102496712A (en) | 2008-01-28 | 2008-01-28 | Fabrication method for lithium battery anode material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011104154503A CN102496712A (en) | 2008-01-28 | 2008-01-28 | Fabrication method for lithium battery anode material |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200810006703XA Division CN101499522B (en) | 2008-01-28 | 2008-01-28 | Anode material of lithium battery and its production method, lithium secondary battery employing the same |
Publications (1)
Publication Number | Publication Date |
---|---|
CN102496712A true CN102496712A (en) | 2012-06-13 |
Family
ID=46188513
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2011104154503A Pending CN102496712A (en) | 2008-01-28 | 2008-01-28 | Fabrication method for lithium battery anode material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102496712A (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060141361A1 (en) * | 2004-12-10 | 2006-06-29 | Toyotaka Yuasa | Positive electrode material for lithium secondary battery, production method thereof, and lithium secondary battery |
JP2006302671A (en) * | 2005-04-20 | 2006-11-02 | Mitsui Mining Co Ltd | Cathode material for lithium-ion secondary battery and its manufacturing method as well as lithium-ion secondary battery using same |
CN101009368A (en) * | 2001-03-20 | 2007-08-01 | 爱克索里奥克斯公司 | Mesoporous network electrode for electrochemical cell |
-
2008
- 2008-01-28 CN CN2011104154503A patent/CN102496712A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101009368A (en) * | 2001-03-20 | 2007-08-01 | 爱克索里奥克斯公司 | Mesoporous network electrode for electrochemical cell |
US20060141361A1 (en) * | 2004-12-10 | 2006-06-29 | Toyotaka Yuasa | Positive electrode material for lithium secondary battery, production method thereof, and lithium secondary battery |
JP2006302671A (en) * | 2005-04-20 | 2006-11-02 | Mitsui Mining Co Ltd | Cathode material for lithium-ion secondary battery and its manufacturing method as well as lithium-ion secondary battery using same |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5072110B2 (en) | Positive electrode material used for lithium battery | |
CN107845830B (en) | Solid electrolyte, lithium battery, battery pack, and vehicle | |
CN101499522B (en) | Anode material of lithium battery and its production method, lithium secondary battery employing the same | |
TWI619298B (en) | Lithium manganese oxide composite, secondary battery, and manufacturing method thereof | |
CN1332461C (en) | Positive electrode active material and non-aqueous electrolyte secondary cell | |
TWI661600B (en) | Lithium-manganese composite oxide, secondary battery, and electric device | |
CN112909238B (en) | Positive active material, positive pole piece and electrochemical energy storage device | |
CN110233247B (en) | Positive active material, positive pole piece and electrochemical energy storage device | |
CN113207314A (en) | Secondary battery, device, artificial graphite and preparation method | |
CN104937749A (en) | Positive electrode for secondary cell, method for manufacturing positive electrode for secondary cell, and whole solid secondary cell | |
JP2012099482A (en) | Positive electrode active material for lithium secondary battery, method of manufacturing positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery, and lithium secondary battery | |
KR20170039648A (en) | Positive-electrode active material, positive electrode, battery, battery pack, electronic device, electric vehicle, electricity storage apparatus, and power system | |
KR20160034799A (en) | Electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery including the same | |
KR102425828B1 (en) | Positive active material, positive electrode and lithium battery containing the material, method of manufacturing the material | |
CN110010903A (en) | Positive pole piece and battery | |
US10629904B2 (en) | Positive electrode active material, positive electrode, battery, battery pack, electronic device, electric vehicle, power storage device, and power system | |
CN114223073A (en) | Negative active material, method of preparing the same, secondary battery, and device including the secondary battery | |
WO2019102319A1 (en) | Secondary battery and secondary battery production method | |
CN115332538A (en) | Hard carbon material, preparation method thereof, electrochemical device and electronic device | |
CN114041226A (en) | Electrochemical device and electronic device comprising same | |
JP2023538082A (en) | Negative electrode and secondary battery containing the same | |
KR100743982B1 (en) | Active material, manufacturing method thereof and lithium secondary battery comprising the same | |
CN116391284A (en) | Electrochemical device and electronic device | |
WO2022133837A1 (en) | Electrochemical device and electronic device | |
CN102496712A (en) | Fabrication method for lithium battery anode material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120613 |