CN101901906A - Lithium ion secondary battery and cathode material prepared by same - Google Patents
Lithium ion secondary battery and cathode material prepared by same Download PDFInfo
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- CN101901906A CN101901906A CN2010102334687A CN201010233468A CN101901906A CN 101901906 A CN101901906 A CN 101901906A CN 2010102334687 A CN2010102334687 A CN 2010102334687A CN 201010233468 A CN201010233468 A CN 201010233468A CN 101901906 A CN101901906 A CN 101901906A
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Abstract
The invention relates to the lithium ion battery field, in particular to a high-capacity cathode material and a high energy density lithium ion secondary battery prepared by the cathode material. The cathode material comprises a cathode active material, an adhesive and a conductive agent, wherein the cathode active material is a composite material of a lithium cobalt oxide active material A and a high nickel active material B; the high nickel active material B is pretreated before mixing; and the mass ratio of the high nickel active material B to the lithium cobalt oxide active material A is between 0.82 and 9. The cathode material can not only prepare the batteries with higher capacity and energy density but also solve the problem of high temperature gas production in the batteries.
Description
Technical field
The present invention relates to the lithium ion battery field, particularly high power capacity positive electrode and use the high energy density lithium ion secondary battery of this material preparation.
Background technology
Lithium rechargeable battery becomes one of the widest secondary cell of range of application owing to have the advantage of high voltage, high-energy-density.The continuous development of portable electric appts microminiaturization, long standby, as the lithium ion battery of power supply, its energy density especially volume energy density constantly promotes, to satisfy the demand of increasingly sharpening.
The positive electrode of using the most ripe energy type lithium rechargeable battery at present is a cobalt acid lithium, under the situation that does not influence battery performance, can reach 4.1g/cc by its its compacted density of anodal diaphragm of forming, and cycle performance excellence, but because its gram volume only is 140mAh/g, further promote its gram volume and may destroy its layer structure, influence discharges and recharges invertibity, and brings very big potential safety hazard.Therefore, cobalt acid lithium can not satisfy the demand of high energy density cells as positive electrode.
And the research that is used to replace the positive electrode of cobalt acid lithium mainly concentrates on and has layer structure and the higher positive electrode of nickel content.These nickelic layer structure positive electrodes and the same hexagonal structure that belongs to of cobalt acid lithium, its gram volume is higher with respect to the sour lithium of cobalt, and actual capacity can reach 180～190mAh/g, but its actual compacted density only is 3.6g/cc.Still there are many problems in the application of nickelic layer structure positive electrode, limiting the main cause that nickelic layer structure positive electrode uses in lithium rechargeable battery is: its high temperature aerogenesis in lithium rechargeable battery, such high temperature aerogenesis can make the flexible packing lithium ion secondary battery volumetric expansion, can make voltage rise height in the box hat lithium rechargeable battery, thereby bring serious potential safety hazard.
Select the nickelic layer structure positive electrode and the cobalt acid lithium of suitable granularity for use, with its mixing, can improve the space availability ratio of anodal diaphragm, the compacted density of the anodal diaphragm that obtains can be near 4.1g/cc, and the lithium of the relative cobalt acid of its gram volume simultaneously has greatly improved.The advantage of comprehensive cobalt acid lithium of mixed material and nickelic layer structure positive electrode, the relative cobalt acid of energy density lithium has greatly improved, make battery with the material that mixes as positive pole, can obtain chemical property, security performance is good, and the higher battery of energy density.As: Chinese patent CN 1848492 discloses a kind of positive electrode, and it comprises positive active material, bonding agent and conductive agent, and wherein positive active material is that cobalt acid lithium is the composite material of active material A and high-nickel material B, and the expression formula of A is Li
xCo
yMa
(1-y)O
2, 0.45≤x≤1.2,0.8≤y≤1 wherein, Ma is Al, Mn, Fe, Mg, Si, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, one or more among Ge and the Ba; The expression formula of B is Li
xNi
aCo
bMb
(1-a-b)O
2, 0.45≤x1≤1.2,0.7≤a≤0.9,0.08≤b≤0.3,0.78≤a+b≤1 wherein, Mb is Al, Mn, Mg, Fe, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, one or more among Ge and the Ba, B/A are 0.04-0.8, its compacted density is greater than 3.7g/cc.Is mixing of active material by high-nickel material with cobalt acid lithium, can make and prepare battery with bigger capacity and higher energy density, promoting high-nickel material and cobalt acid lithium is the mixed proportion of active material, help promoting the capacity and the energy density of battery, high-nickel material and cobalt acid lithium are the reduction that the lifting of active material ratio depends on the high temperature aerogenesis of high-nickel material in battery.But Chinese patent CN 1848492 can't solve the problem of the high temperature aerogenesis of high-nickel material in battery, Gu the ratio of its nickelic positive electrode can not be too high, i.e. the weight ratio of high-nickel material and cobalt acid lithium is 0.04～0.8, and ratio is less than normal.Because the gram volume of high-nickel material is bigger than the gram volume of the sour lithium of cobalt, the little direct influence of the content of high-nickel material mixes the effect that back positive electrode gram volume promotes, and it is limited to make that energy density promotes.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of positive electrode of lithium rechargeable battery is provided, it can prepare the battery with bigger capacity and higher energy density, can solve the problem of the high temperature aerogenesis in the battery again.
In order to realize above-mentioned purpose, the present invention by the following technical solutions:
A kind of positive electrode of lithium rechargeable battery, it contains positive active material, bonding agent and conductive agent, and wherein positive active material is that cobalt acid lithium is the composite material of active material A and high nickel hydroxide active material B, and cobalt acid lithium is that the expression formula of active material A is Li
xCo
yMa
(1-y)O
2, 0.45≤x≤1.2,0.8≤y≤1 wherein, Ma is one or more among Al, Mn, Fe, Mg, Si, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and the Ba; The expression formula of high nickel hydroxide active material B is Li
X1Ni
aCo
bMb
(1-a-b)O
2, 0.45≤x1≤1.2,0.7≤a≤0.9,0.08≤b≤0.3,0.78≤a+b≤1 wherein, Mb is one or more among Al, Mn, Mg, Fe, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and the Ba; Through preliminary treatment, the mass ratio B/A that described cobalt acid lithium is active material A and high nickel hydroxide active material B is between 0.82～9 before mixing for described high nickel hydroxide active material B.
It is that active material A and high nickel hydroxide active material B mass ratio B/A are 0.82～9 that the present invention adopts cobalt acid lithium, improve the content of high nickel hydroxide active material B greatly, not only comprehensive cobalt acid lithium is active material A high compacted density but also has the characteristics of high nickel hydroxide active material B high power capacity, two kinds of active substance combination are become the more positive electrode of high-energy-density, simultaneously, before mixing, high nickel hydroxide active material B is carried out preliminary treatment, overcome the shortcoming of high nickel hydroxide active material B high temperature aerogenesis in battery, make the battery that obtains not only have higher energy density, and high-temperature storage performance and security performance can meet the demands.
For capacity and the energy density that promotes the ratio of high nickel hydroxide active material B, make the lithium rechargeable battery of preparing further promoted, the present invention has carried out preliminary treatment to high nickel hydroxide active material B, can obviously reduce high-nickel material high temperature aerogenesis in battery.
Wherein, high nickel hydroxide active material B the preliminary treatment of process be that the surface coats, coat the oxide of last layer M on high nickel hydroxide active material B surface, M is any one among Mg, Al, Zr, Zn, Ti, Cu, the B.
Coating can adopt liquid phase deposition to coat: high nickel hydroxide active material B is dropped in the solution of the compound that contains the M element (solvent is water or ethanol), in solution, add a kind of solution for example ammoniacal liquor, carbonic hydroammonium, nitrate solution or the like again, make the M element form precipitation or colloidal sol.Wait by temperature, pH value, the reaction time of regulator solution then and control reaction rate and covering amount, make high nickel hydroxide active material B surface coat the compound of last layer M equably.Carry out Separation of Solid and Liquid with coating high nickel hydroxide active material B later, under 80～100 ℃ temperature, dry, under 300～900 ℃ temperature, carry out roasting 2～10h again, finally make high nickel hydroxide active material B surface coat the oxide of one deck M equably.Can certainly adopt other method for coating, as long as can make high nickel hydroxide active material B surface coat the oxide of one deck M equably.
Wherein, high nickel hydroxide active material B the preliminary treatment of process in deionized water, to clean, carry out Separation of Solid and Liquid (can adopt centrifugal mode and water to carry out Separation of Solid and Liquid) with cleaning high nickel hydroxide active material B later, the higher nickel hydroxide active material B vacuum bakeout after the Separation of Solid and Liquid is removed moisture.Wherein, the pH value of described deionized water is between 5.5～7, the weight ratio of high nickel hydroxide active material B and deionized water is between 1: 2～1: 10, scavenging period is between 1～20 minute, baking temperature is 80～150 ℃, the baking vacuum pressure is less than 100Pa, and stoving time is 10～20H, to remove the moisture among the high nickel hydroxide active material B.
Wherein, in order to make the positive electrode after mixing have higher compacted density, cobalt acid lithium is that the average grain diameter of active material A and the average grain diameter of high nickel hydroxide active material B need to optimize, the average grain diameter D50 that the sour lithium of cobalt is active material A is between 15～22 μ m, the average grain diameter D50 of B is between 8～14 μ m, the ratio of the D50 of A and B is between 1.07～2.75, and indication average grain diameter D50 reaches 50% o'clock pairing particle diameter for adopting the measured cumulative particle sizes volume distributed median percentage of laser diffraction and scattering type particles distribution instrument.
Wherein, the compacted density of the positive electrode of a kind of lithium rechargeable battery of the present invention is between active material A and the high nickel hydroxide active material B between cobalt acid lithium, and more than or equal to 3.7g/cc.
Wherein, described cobalt acid lithium is that the mass ratio B/A of active material A and high nickel hydroxide active material B is between 1.5～9.
Wherein, described cobalt acid lithium is that the mass ratio B/A of active material A and high nickel hydroxide active material B is 1.67.
Wherein, described cobalt acid lithium is that active material A is the LiCoO2 of 18 μ m for average grain diameter D50, and high nickel hydroxide active material B is the Li of 12 μ m for average grain diameter D50
1.02Ni
0.78Co
0.20Al
0.02O
2
Another object of the present invention is to provide a kind of lithium rechargeable battery of high-energy-density.
In order to realize above-mentioned purpose, the present invention by the following technical solutions:
A kind of lithium rechargeable battery comprises positive pole, negative pole, electrolyte and barrier film, and described just very above-mentioned cobalt acid lithium is the composite material of active material A and high nickel hydroxide active material B, and its mass ratio B/A is between 0.82～9.
Of the present invention have bigger capacity and higher energy density, and battery can not have the good high-temperature memory property owing to safety problem takes place the high temperature aerogenesis.
Description of drawings
Fig. 1 is that anodal diaphragm compacted density of the embodiment of the invention and Comparative Examples and positive active material gram volume are the variation relation figure of the mass ratio B/A of active material A with high nickel hydroxide active material B and cobalt acid lithium;
Fig. 2 is that the embodiment of the invention and Comparative Examples battery capacity are the variation relation figure of the mass ratio B/A of active material A with high nickel hydroxide active material B and cobalt acid lithium;
Fig. 3 is that the embodiment of the invention and Comparative Examples energy content of battery density are the variation relation figure of the mass ratio B/A of active material A with high nickel hydroxide active material B and cobalt acid lithium;
Fig. 4 is the variation relation figure of the mass ratio B/A of active material A for the thickness swelling of the embodiment of the invention and 85 ℃/4h of Comparative Examples storage back battery with high nickel hydroxide active material B and cobalt acid lithium.
Embodiment
Below in conjunction with the drawings and specific embodiments, the characteristics of lithium rechargeable battery of the present invention and positive electrode thereof are described.
Lithium rechargeable battery involved in the present invention has following positive pole: by on the one or both sides of plane of bringing into play the collector function or netted conductive substrates, form and contain the anodal diaphragm that positive active material, conductive agent and binding agent constitute.
The active material of above-mentioned anodal diaphragm is that cobalt acid lithium is the composite material of active material A and high nickel hydroxide active material B.Cobalt acid lithium is that the expression formula of active material A is Li
xCo
yMa
(1-y)O
2, 0.45≤x≤1.2,0.8≤y≤1 wherein, Ma is one or more among Al, Mn, Fe, Mg, Si, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and the Ba; The x value of representing lithium content in the above-mentioned active material when discharging and recharging between 0.95～1.2, the x value of this moment conference cause the lithium impurity content to increase, the too small performance that can influence battery capacity of x value, so preferably and between 1.0～1.2.Along with lithium ion in the charging process is deviate to negative pole to move, the x value constantly reduces, but after the x value is reduced to a certain degree, can cause the positive active material material structure to be destroyed, and reduces the invertibity that discharges and recharges, so the x value should be greater than 0.45.Therefore, preferred x value is between 0.45～1.2.
The expression formula of high nickel hydroxide active material B is Li
X1Ni
aCo
bMb
(1-a-b)O
2, 0.45≤x1≤1.2,0.7≤a≤0.9,0.08≤b≤0.3,0.78≤a+b≤1 wherein, Mb is one or more among Al, Mn, Mg, Fe, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and the Ba; Represent a value of nickel content to determine its gram volume performance among the above-mentioned high nickel hydroxide active material B, the value of a is little, can cause its gram volume lower, with respect to cobalt acid lithium based material, capacity promotes limited, and a value is excessive, can cause its material structure instability, therefore be preferable between 0.7～0.9.Represent the b value of cobalt content too small, can make the load character variation of material, if the b value is excessive, can cause the rising of material cost, the gram volume performance can reduce in addition, therefore is preferable between 0.08～0.3.Doped chemical Mb has played the effect of stable high-nickel material structure, preferred Al and Mn, and its content (1-a-b) is preferable between 0.01～0.1.
The ratio of the weight that the sour lithium of high nickel hydroxide active material B and cobalt is active material A in the above-mentioned positive electrode is between 0.82～9, high nickel hydroxide active material B content is low excessively, can make the composite material gram volume bring into play the advantage that loses for the sour lithium based material of cobalt, the too high levels of high nickel hydroxide active material B, can cause the composite material compacted density low excessively, influence the energy density of battery, and battery aerogenesis phenomenon in the high temperature storage process is serious, causes battery failure.
The compacted density of above-mentioned anodal diaphragm is preferable over more than or equal to 3.75g/cc more than or equal to 3.7g/cc.In order to make anodal diaphragm reach bigger compacted density, can by reduce pressure roll gap, increase pressure roller pressure, pressure roll rotating speed and improve modes such as pressure roll temperature and realize slows down.Here the compacted density of anodal diaphragm is measured by the following method.Cut anodal diaphragm disk (being no more than 24 hours and not process heated baking processing) through overcompaction time of repose later through certain area of overcompaction, adopting minimum scale is the anodal disk quality of electronic balance weighing of 1mg, deduct collector weight of the same area, thereby obtain the weight of anodal diaphragm.That face of the opposing party is that the spiral micrometer of 0.001mm is measured anodal diaphragm thickness with minimum scale, the thickness of deduction collector, thus draw the thickness of anodal diaphragm.Subsequently, the quality of anodal and basic unit divided by its volume, is just obtained the compacted density of anodal diaphragm.
The conductive agent that contains in the above-mentioned anodal diaphragm preferably with material with carbon elements such as carbon black, acetylene black, graphite, carbon fiber, carbon nano-tube, should have smaller particles degree 10～5000 μ m, and bigger specific area, the BET of conductive agent (specific area) is at least more than 20 times of mixed active material (high nickel hydroxide active material B and cobalt acid lithium are active material A).Bonding agent in the above-mentioned anodal diaphragm can be selected Kynoar based polymer (as PVDF), rubber based polymer (as SBR) etc. for use.
The collector of above-mentioned anode pole piece can be selected metallicity electric conducting materials such as the aluminium, stainless steel, titanium of netted or dull and stereotyped paper tinsel shape for use, and thickness is preferable over 8～20 μ m.Available now on behalf of known coating method-as extrusion coated, transfer coated etc.) will contain above-mentioned anode sizing agent (positive active material, bonding agent and conductive agent and stirring solvent are formed) and be coated on the collector, form anode pole piece through behind the high-temperature baking.Above-mentioned anode sizing agent viscosity should be between 1000～7000mPaS, so that anode sizing agent can be coated on the collector equably.
Among the present invention as the active material of negative pole be can removal lithium embedded material with carbon element, silicon-base alloy or both mixing.Wherein material with carbon element can be in hard carbon material, soft material with carbon element, native graphite, Delanium, carbonaceous mesophase spherules, the micron carbon fiber one or more.Bonding agent in the cathode membrane can select for use butadiene-styrene rubber based polymer (as SBR), cellulose-based polymer (as CMC), Kynoar based polymer as (PVDF) etc.Because the negative electrode active material material has the good electron transport properties, so can comprise or not comprise conductive agent in the cathode membrane, close in selected conductive agent and the positive electrode.Can select for use as the collector of negative pole but be not limited to netted or paper tinsel shape copper, its thickness preferably with 6～10 μ m.
Availablely will contain above-mentioned cathode size (negative electrode active material, solvent, bonding agent and/or conductive agent stir and form) on behalf of known coating method (as extrusion coated, transfer coated etc.) now and be coated on the negative current collector, form cathode pole piece through behind the high-temperature baking.Above-mentioned cathode size viscosity should be between 500～4000mPaS, so that cathode size can be coated on the collector equably.
Lithium rechargeable battery of the present invention can followingly be made: welding conduction lug on above-mentioned positive pole and cathode pole piece, and will accompany the anode pole piece of barrier film and cathode pole piece in the centre and be rolled into helical form and form naked electric core, the packaging bag that naked electric core is put into box hat (as 18650 type cylinder box hats) or is made up of aluminium plastic composite material, inject nonaqueous electrolytic solution, seal and make.
Above-mentioned barrier film can be selected microporous polyethylene, polypropylene or its laminated film for use, and preferred thickness is between 8～20 μ m.Organic solvent in the above-mentioned nonaqueous electrolytic solution is not particularly limited, and can select the mixing of one or more cyclic carboxylic esters and wire carboxylate for use, as PC (propene carbonate) and EC (ethylene carbonate) and DEC
The mixing of (diethyl carbonate), and the solute of non-aqueous solution electrolysis liquid can be selected fluorine-containing lithium salts such as lithium hexafluoro phosphate (LiPF6) etc. for use, the concentration of lithium salts is between 0.6～1.4mol/L in the electrolyte.
Embodiment 1:
Anodal making
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and promptly particle diameter is less than the LiCoO of 18 μ m
2Particle volume accounts for 50% of total particle cumulative volume; Using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B, promptly particle diameter is less than the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2Particle volume accounts for 50% of total particle volume.High nickel hydroxide active material B through the washing of 15min deionized water, removes the purpose that contains lithium impurity (as lithium carbonate, lithium hydroxide etc.) to reach before mixing, through centrifugal back under 100 ℃, vacuum pressure less than in the 100Pa vacuum dry 20 hours to remove moisture.Regulating high nickel hydroxide active material B and cobalt acid lithium is that the weight ratio B/A of active material A is 0.82.And modulation contains the slurry of this active material, the solid constituent of this slurry comprises 95.5% active material, 2.2% conductivity auxiliary agent (conductive carbon) and 2.3% bonding agent (PVDF), this slurry use NMP as solvent, and the weight of solvent accounts for 30% of total slurry weight.This slurry is coated in the Al paper tinsel two sides of 12 μ m equably, utilizes roll squeezer to roll processing subsequently, the compacted density that obtains anodal diaphragm is 4.0g/cc.
The making of negative pole
Use BET (specific area) to be 3.15m
2The Delanium of/g is as negative electrode active material.Modulation contains the slurry of this active material, and the solid constituent of this slurry comprises this negative electrode active material of 95.8%, and 3.2% SBR (styrene butadiene rubber) and CMC (sodium carboxymethylcellulose) are as bonding agent, and 1% conductive carbon is as the conductivity auxiliary agent.This slurry makes water as solvent, and the weight of solvent accounts for 55% of total slurry weight.This slurry is coated in the Cu paper tinsel two sides of 8 μ m equably, utilizes roll squeezer to roll processing subsequently, the compacted density that obtains cathode membrane is 1.65g/cc.
The assembling of battery
Welding conduction lug on anodal and cathode pole piece, make anodal and negative pole centre accompany the PP/PE composite isolated film of 16 μ m and overlapping, in the aluminium plastic composite material packaging bag of packing into after its coiling city helical form, packaging bag thickness is 115 μ m, inject nonaqueous electrolytic solution, seal the back battery is changed into, treat to extract the gas in the packaging bag out and excise unnecessary packaging bag behind the abundant aerogenesis of both positive and negative polarity, obtain being of a size of the battery of the high 80.8mm of the wide 33.58mm of thick 4.13mm.The electrolyte of above-mentioned battery is the LiPF6 solution of 1mol/L, and primary solvent is mixed by EC, PC, DEC.
Embodiment 2
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B is through the same preprocess method of embodiment 1, but through centrifugal back under 80 ℃, vacuum pressure less than in the 100Pa vacuum dry 15 hours to remove moisture.Regulating high nickel hydroxide active material B and cobalt acid lithium is that the weight ratio B/A of active material A is 1.67.And make anodal diaphragm compacted density change to 3.9g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B is through the same preliminary treatment of embodiment 1, and the weight ratio B/A that to regulate the sour lithium of high nickel hydroxide active material B and cobalt be active material A is 3.And make anodal diaphragm compacted density change to 3.8g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 4
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B is through the same preliminary treatment of embodiment 2, and the weight ratio B/A that to regulate the sour lithium of high nickel hydroxide active material B and cobalt be active material A is 9.And make anodal diaphragm compacted density change to 3.75g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 11 μ m
0.98Ni
0.77Co
0.20Al
0.01Mn
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B is through the same preliminary treatment of embodiment 2, and the weight ratio B/A that to regulate the sour lithium of high nickel hydroxide active material B and cobalt be active material A is 1.67.And make anodal diaphragm compacted density change to 3.9g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 6
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 13 μ m
1.07Ni
0.78Co
0.20O
2As high nickel hydroxide active material B, high nickel hydroxide active material B is through the same preliminary treatment of embodiment 1, and the weight ratio B/A that to regulate the sour lithium of high nickel hydroxide active material B and cobalt be active material A is 1.67.And make anodal diaphragm compacted density change to 3.9g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 7
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 13 μ m
1.00Ni
0.83Co
0.17O
2As high nickel hydroxide active material B, high nickel hydroxide active material B is through the same preliminary treatment of embodiment 1, and the weight ratio B/A that to regulate the sour lithium of high nickel hydroxide active material B and cobalt be active material A is 1.67.And make anodal diaphragm compacted density change to 3.9g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 8
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 15 μ m
0.81Ni
0.83Co
0.14Al
0.03O
2As high nickel hydroxide active material B, high nickel hydroxide active material B is through the same preliminary treatment of embodiment 1, and the weight ratio B/A that to regulate the sour lithium of high nickel hydroxide active material B and cobalt be active material A is 1.67.And make anodal diaphragm compacted density change to 3.9g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 13 μ m
0.99Ni
0.75Co
0.24Al
0.01O
2As high nickel hydroxide active material B, high nickel hydroxide active material B is through the same preliminary treatment of embodiment 1, and the weight ratio B/A that to regulate the sour lithium of high nickel hydroxide active material B and cobalt be active material A is 1.67.And make anodal diaphragm compacted density change to 3.9g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Table 1: to adopt different high nickel hydroxide active material B and cobalt acid lithium be active material A according to B/A is the gram volume that 1.67 the prepared anodal diaphragm of ratio is brought into play.
Embodiment 10
Using average grain diameter D50 is the Li of 22 μ m
1.05Co
0.99Mg
0.01O
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2LiNi
0.78Co
0.19Al
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B is through the same preliminary treatment of embodiment 1, and the weight ratio B/A that to regulate the sour lithium of high nickel hydroxide active material B and cobalt be active material A is 1.67.And make anodal diaphragm compacted density change to 4.0g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 11
Using average grain diameter D50 is the Li of 17 μ m
1.15CoO
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2LiNi
0.78Co
0.19Al
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B is through the same preliminary treatment of embodiment 1, and the weight ratio B/A that to regulate the sour lithium of high nickel hydroxide active material B and cobalt be active material A is 1.67.And make anodal diaphragm compacted density change to 4.0g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Table 2: to adopt different cobalt acid lithium be active material A and high nickel hydroxide active material B according to B/A is gram volume, average grain diameter D50 and the compacted density of the prepared anodal diaphragm of 1.67 ratio.
Different as can be seen D50 cobalts acid lithiums are active material A in the table 2 has bigger influence to the compacted density of mixed anodal diaphragm.
Embodiment 12
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B.High nickel hydroxide active material B has coated one deck ZrO by the mode of liquid deposition on the surface
2, regulating high nickel hydroxide active material B and cobalt acid lithium is that the weight ratio B/A of active material A is 1.67.And make anodal diaphragm compacted density change to 3.9g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Active material B surface is coated ZrO
2Mode as follows: contain 1mol KZrF at 20L
6And 10molLiNO
3The aqueous solution in add 10kg Li
1.02Ni
0.78Co
0.20Al
0.02O
2, the ammoniacal liquor adjusting pH value that adds 0.5mol/L is 8, stirs 15min under 60 ℃ temperature fast, adopts centrifuge with Li subsequently
1.02Ni
0.78Co
0.20Al
0.02O
2Sample separation is come out, 80 ℃ dry 10 hours down, 750 ℃ roasting temperature 2 hours, finally obtain the surface and be coated with ZrO again
2Li
1.02Ni
0.78Co
0.20Al
0.02O
2Material.
Embodiment 13
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B.High nickel hydroxide active material B has coated one deck Al by the mode of liquid deposition on the surface
2O
3, regulating high nickel hydroxide active material B and cobalt acid lithium is that the weight ratio B/A of active material A is 1.67.And make anodal diaphragm compacted density change to 3.9g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Active material B surface is coated Al
2O
3Mode as follows: contain 1mol Al (NO at 20L
3)
3With 10mol LiNO
3The aqueous solution in add 10kg Li
1.02Ni
0.78Co
0.20Al
0.02O
2, the ammoniacal liquor adjusting pH value that adds 5mol/L is 6, stirs 15min under 45 ℃ temperature fast, adopts centrifuge with Li subsequently
1.02Ni
0.78Co
0.20Al
0.02O
2Sample separation is come out, 80 ℃ dry 10 hours down, 750 ℃ roasting temperature 2 hours, finally obtain the surface and be coated with Al again
2O
3Li
1.02Ni
0.78Co
0.20Al
0.02O
2Material.
Embodiment 14
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B.High nickel hydroxide active material B has coated layer of ZnO by the mode of liquid deposition on the surface
2, regulating high nickel hydroxide active material B and cobalt acid lithium is that the weight ratio B/A of active material A is 1.67.And make anodal diaphragm compacted density change to 3.9g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
With active material B surface clading ZnO
2Mode as follows: contain 0.5mol ZnF at 20L
2And 10molLiNO
3The aqueous solution in add 10kg Li
1.02Ni
0.78Co
0.20Al
0.02O
2, under 45 ℃ temperature, stir 30min fast, adopt centrifuge with Li subsequently
1.02Ni
0.78Co
0.20Al
0.02O
2Sample separation is come out, 80 ℃ dry 10 hours down, 750 ℃ roasting temperature 2 hours, finally obtain the surface and be coated with ZnO again
2Li
1.02Ni
0.78Co
0.20Al
0.02O
2Material.
Embodiment 15
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B.High nickel hydroxide active material B has coated one deck TiO by the mode of liquid deposition on the surface
2, regulating high nickel hydroxide active material B and cobalt acid lithium is that the weight ratio B/A of active material A is 1.67.And make anodal diaphragm compacted density change to 3.9g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Active material B surface is coated TiO
2Mode as follows: contain 0.2mol butyl titanate Ti (OBu) at 20L
4Ethanolic solution in add 10kg Li
1.02Ni
0.78Co
0.20Al
0.02O
2, in solution, slowly add 0.5kg water, under 25 ℃ temperature, stir 30min fast, adopt centrifuge with Li subsequently
1.02Ni
0.78Co
0.20Al
0.02O
2Sample separation is come out, and 80 ℃ of following vacuumizes 10 hours, vacuum pressure was less than 100Pa, 750 ℃ roasting temperature 2 hours, finally obtains the surface and is coated with TiO again
2Li
1.02Ni
0.78Co
0.20Al
0.02O
2Material.
Table 3: the high nickel hydroxide active material B that adopts different surfaces to coat to handle and lithium-cobalt system cobalt acid lithium be active material A proportionally B/A be that the gram volume of the prepared anodal diaphragm of 1.67 ratio is brought into play and the prepared full battery of the 4.2V thickness swelling after through 85 ℃/4h high temperature storage.
As can be seen from Table 3: the battery process that contains through the high nickel hydroxide active material B after the coating processing of surface obviously reduces through the thickness change before and after the 85 ℃/4h high temperature storage.
Comparative example 1
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material, and makes the compacted density of anodal diaphragm reach 4.1g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Comparative example 2
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B is through the same preliminary treatment of embodiment 1, and the weight ratio B/A that to regulate the sour lithium of high nickel hydroxide active material B and cobalt be active material A is 0.5.And make anodal diaphragm compacted density change to 4.0g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Table 4: the compacted density of the anodal diaphragm of each mixed proportion and the performance of the gram volume in lithium rechargeable battery.
In conjunction with Fig. 1 and table 4 as can be seen: along with high nickel hydroxide active material B and cobalt acid lithium are the increase of active material A mass ratio B/A, though the compacted density of anodal diaphragm can reduce gradually, the gram volume of positive active material but can increase gradually.
Table 5: the thickness swelling of average size performance, average discharge volt, average cell energy density and the battery of lithium rechargeable battery of anodal preparing diaphragm that adopts each mixed proportion after through 85 ℃/4h high temperature storage.
Discharge capacity when listed capacity is 30 ℃ in the table 5 under the discharge-rate of 0.2C, when listed average discharge volt is 30 ℃ at the discharge energy of 0.2C and the ratio of discharge capacity.Thickness swelling in the table after the listed 85 ℃/4h high temperature storage is that battery completely is charged to behind the 4.2V through the thickness change before and after the 85 ℃/4h high temperature storage.In conjunction with Fig. 2-3 and table 5 as can be seen: capacity that the positive active material of different B/A ratio is finally showed in lithium secondary battery and volume energy density are along with the trend that afterwards reduces appears increasing earlier in the increase of B/A.In conjunction with Fig. 4, the thickness swelling after the 85 ℃/4h high temperature storage increases with the increase of B/A, but all less than 13%, meets the battery safety requirement.
Comparative example 3
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B does not pass through preliminary treatment, and regulating high nickel hydroxide active material B and cobalt acid lithium is that the weight ratio B/A of active material A is 0.5.And make anodal diaphragm compacted density change to 4.00g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Comparative example 4
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B does not pass through preliminary treatment, and regulating high nickel hydroxide active material B and cobalt acid lithium is that the weight ratio B/A of active material A is 0.82.And make anodal diaphragm compacted density change to 4.0g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Comparative example 5
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B does not pass through preliminary treatment, and regulating high nickel hydroxide active material B and cobalt acid lithium is that the weight ratio B/A of active material A is 1.67.And make anodal diaphragm compacted density change to 3.9g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Comparative example 6
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B does not pass through preliminary treatment, and regulating high nickel hydroxide active material B and cobalt acid lithium is that the weight ratio B/A of active material A is 3.And make anodal diaphragm compacted density change to 3.8g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Comparative example 7
Using average grain diameter D50 is the LiCoO of 18 μ m
2As cobalt acid lithium is active material A, and using average grain diameter D50 is the Li of 12 μ m
1.02Ni
0.78Co
0.20Al
0.02O
2As high nickel hydroxide active material B, high nickel hydroxide active material B does not pass through preliminary treatment, and regulating high nickel hydroxide active material B and cobalt acid lithium is that the weight ratio B/A of active material A is 9.And make anodal diaphragm compacted density change to 3.75g/cc.In addition, make lithium rechargeable battery similarly to Example 1.
Table 6: the thickness swelling of average size performance, average discharge volt, average cell energy density and the battery of lithium rechargeable battery of anodal preparing diaphragm that adopts each mixed proportion after through 85 ℃/4h high temperature storage.
In conjunction with Fig. 4 and table 6 as can be seen: the battery that contains through pretreated high nickel hydroxide active material B increases obviously through the thickness change before and after the 85 ℃/4h high temperature storage, and can't satisfy the requirement of battery safety.
Use the capacity of positive electrode active materials prepared cell of the present invention with respect to prior art very large lifting (generally having promoted more than 4.5%) to be arranged from the foregoing description, energy density also has very large raising (generally having improved more than 2.9%) with respect to prior art.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also carry out suitable change and modification to above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms do not constitute any restriction to the present invention just for convenience of description.
Claims (10)
1. the positive electrode of a lithium rechargeable battery, it contains positive active material, bonding agent and conductive agent, and wherein positive active material is that cobalt acid lithium is the composite material of active material A and high nickel hydroxide active material B,
Cobalt acid lithium is that the expression formula of active material A is Li
xCo
yMa
(1-y)O
2, 0.45≤x≤1.2,0.8≤y≤1 wherein, Ma is one or more among Al, Mn, Fe, Mg, Si, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and the Ba;
The expression formula of high nickel hydroxide active material B is Li
X1Ni
aCo
bMb
(1-a-b)O
2, 0.45≤x1≤1.2,0.7≤a≤0.9,0.08≤b≤0.3,0.78≤a+b≤1 wherein, Mb is one or more among Al, Mn, Mg, Fe, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and the Ba;
It is characterized in that: through preliminary treatment, the mass ratio B/A that described cobalt acid lithium is active material A and high nickel hydroxide active material B is between 0.82～9 before mixing for described high nickel hydroxide active material B.
2. the positive electrode of a kind of lithium rechargeable battery according to claim 1, it is characterized in that: high nickel hydroxide active material B the preliminary treatment of process coat for the surface, coat the oxide of last layer M on high nickel hydroxide active material B surface, M is any one among Mg, Al, Zr, Zn, Ti, Cu, the B.
3. the positive electrode of a kind of lithium rechargeable battery according to claim 1, it is characterized in that: high nickel hydroxide active material B the preliminary treatment of process in deionized water, to clean, carry out Separation of Solid and Liquid with cleaning high nickel hydroxide active material B later, the higher nickel hydroxide active material B vacuum bakeout after the Separation of Solid and Liquid is removed moisture.
4. the positive electrode of a kind of lithium rechargeable battery according to claim 3, it is characterized in that: the pH value of described deionized water is between 5.5～7, the weight ratio of high nickel hydroxide active material B and deionized water is between 1: 2～1: 10, scavenging period is between 1～20 minute, baking temperature is 80～150 ℃, the baking vacuum pressure is less than 100Pa, and stoving time is 10～20H.
5. the positive electrode of a kind of lithium rechargeable battery according to claim 1, it is characterized in that: the average grain diameter D50 that the sour lithium of cobalt is active material A is between 15～22 μ m, the average grain diameter D50 of B is between 8～14 μ m, and the ratio of the D50 of A and B is between 1.07～2.75.
6. the positive electrode of a kind of lithium rechargeable battery according to claim 1, it is characterized in that: its compacted density is more than or equal to 3.7g/cc.
7. according to the positive electrode of any described a kind of lithium rechargeable battery of claim 1-6, it is characterized in that: the mass ratio B/A that described cobalt acid lithium is active material A and high nickel hydroxide active material B is between 1.5～9.
8. the positive electrode of a kind of lithium rechargeable battery according to claim 7 is characterized in that: the mass ratio B/A that described cobalt acid lithium is active material A and high nickel hydroxide active material B is 1.67.
9. according to the positive electrode of any described a kind of lithium rechargeable battery of claim 1-6, it is characterized in that: described cobalt acid lithium is that active material A is the LiCoO2 of 18 μ m for average grain diameter D50, and high nickel hydroxide active material B is the Li of 12 μ m for average grain diameter D50
1.02Ni
0.78Co
0.20Al
0.02O
2
10. a lithium rechargeable battery comprises positive pole, negative pole, electrolyte and barrier film, it is characterized in that: any one positive electrode of described just very claim 1-9.
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