CN102315428B - Preparation method for anode material - Google Patents
Preparation method for anode material Download PDFInfo
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- CN102315428B CN102315428B CN2010102188568A CN201010218856A CN102315428B CN 102315428 B CN102315428 B CN 102315428B CN 2010102188568 A CN2010102188568 A CN 2010102188568A CN 201010218856 A CN201010218856 A CN 201010218856A CN 102315428 B CN102315428 B CN 102315428B
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- positive electrode
- high temperature
- temperature inert
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- swelling agent
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010405 anode material Substances 0.000 title abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 238000005245 sintering Methods 0.000 claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000036961 partial effect Effects 0.000 claims abstract description 5
- 230000008961 swelling Effects 0.000 claims description 40
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 2
- 206010021143 Hypoxia Diseases 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical class [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017270 Ni0.8Co0.2(OH)2 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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 belongs to the technical field of lithium ion batteries and particularly discloses a preparation method for an anode material. The method comprises the steps of: mixing anode material precursors with a lithium source and high-temperature inert expanding agent, then sintering the mixture at high temperature under an oxygen-containing atmosphere and finally removing the high-temperature inert expanding agent. The melting starting temperature of the high-temperature inert expanding agent is higher than 800 DEG C. The ratio of the volume of the high-temperature inert expanding agent at 700 DEG C to the volume of the high-temperature inert expanding agent at 25 DEG C is larger than 2. The method disclosed by the invention effectively eliminates the problem of partial oxygen deficiency of the material caused by material agglomeration during sintering and thereby improves the specific capacity and the cycling performance of the anode material.
Description
Technical field
The invention belongs to technical field of lithium ion, relate in particular to a kind of preparation method of positive electrode.
Background technology
But lithium ion battery has the operating voltage height, specific energy is large, lightweight, volume is little, have extended cycle life, memory-less effect fast charging and discharging and the advantage such as pollution-free, and is widely used in each electronic product.Positive electrode is as the important component part of lithium ion battery, and the quality of its performance plays decisive role to performance of lithium ion battery.Positive electrode the most commonly used is the positive electrode of nickel manganese cobalt series.
In the prior art, the preparation method of the positive electrode of lithium ionic cell nickel manganese cobalt series is generally: high temperature solid phase synthesis, the precipitation method, sol-gel process, spray drying process etc.Wherein be preferably the precipitation method and spray drying process.These two kinds of methods all are to synthesize first positive electrode presoma (being the hydroxide of nickel manganese cobalt), and then the sintering under oxygen atmosphere with positive electrode presoma and lithium source finally forms positive electrode.
But, in the sintering process, because temperature is higher, the reaction raw materials particle produces agglomeration easily, particle and particle are bonded together mutually, spread in the reaction raw materials particle thereby suppressed oxygen, thereby have reduced reactivity, it is insufficient finally to cause reaction to be carried out, and exists the phenomenon that does not have on a small quantity oxidation to exist.Make the positive electrode heterogeneity, overall performance descends, and can reduce specific capacity and the cycle performance of material.
And by adding the methods such as agitating device, the anoxic problem that causes because of reunion in the time of can not effectively solving sintering.This is because paddle can only destroy interior in a big way agglomeration, and the agglomeration is not among a small circle acted on; The problem that therefore also can have local anoxic.The a series of problems such as and paddle also can bring impurity, and appliance arrangement is complicated, adds energy consumption, and cost is large.
Summary of the invention
Technical problem to be solved by this invention is: in the prior art, sintering process is insufficient, the phenomenon of the inner anoxic of local material; Thereby provide a kind of sintering abundant, the method for preparing anode material that the positive electrode overall performance is good.
A kind of preparation method of positive electrode, it comprises: the positive electrode presoma is mixed with lithium source, high temperature inert swelling agent, and then high temperature sintering under oxygen-containing atmosphere separates the high temperature inert swelling agent and removes;
The general formula of described positive electrode presoma is M
aX
b(OH)
2, wherein, 0.8≤a≤1,0≤b≤0.2, M is selected among Ni, Mn, the Co one or more, and X is metal-doped element, and X is selected from Fe, Al, Mg, Cr, Sr, Ti or the rare earth element one or more;
The fusing initial temperature of described high temperature inert swelling agent is greater than 800 ℃, and volume ratio is greater than 2 during its 700 ℃ of described high temperature inert swelling agents and 25 ℃ the time.
The present inventor learns through a large amount of experiment and analyses, sintering basic reason incomplete, material internal anoxic problem is in the prior art: the raw materials self such as positive electrode presoma, lithium source are at high temperature reunited, form the oxygen insulating course, cause sintering insufficient.The present inventor is unexpected to be found, adds high temperature inert expanding material particle, mixes then sintering with the reaction raw materials particle.This high temperature inert expanding material particle keeps solid under sintering temperature, and has higher expansion character.When sintering, this high-temperature expansion material granule keeps reactionlessness, does not react with the reaction raw materials particle, can not introduce the problems such as impurity simultaneously.The favorable reproducibility of the positive electrode of preparation, homogeneity is high, and overall performance is superior.The present inventor infers its reason: when high temperature sintering, high temperature inert expanding material itself evenly mixes with reaction raw materials, and the high temperature inert expanding material has disperseed reaction raw materials, and the reunion of reaction raw materials is had certain inhibitory action.Further, the high temperature inert swelling agent has good extensibility, to the certain active force of reaction raw materials on every side, the reunion between the reaction material is inhibited at stretching process.Increased the space between the reaction raw materials so that oxygen molecule by void diffusion in reaction raw materials, be conducive to enlarge the reactivity area.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
A kind of preparation method of positive electrode, it comprises: the positive electrode presoma is mixed with lithium source, high temperature inert swelling agent, and then high temperature sintering under oxygen-containing atmosphere separates the high temperature inert swelling agent and removes;
The general formula of described positive electrode presoma is M
aX
b(OH)
2, wherein, 0.8≤a≤1,0≤b≤0.2, M is selected among Ni, Mn, the Co one or more, and X is metal-doped element, and X is selected from Fe, Al, Mg, Cr, Sr, Ti or the rare earth element one or more;
The fusing initial temperature of described high temperature inert swelling agent is greater than 800 ℃, and volume ratio is greater than 2 during its 700 ℃ of described high temperature inert swelling agents and 25 ℃ the time.
Wherein, the positive electrode presoma is for will prepare hydroxide corresponding to positive electrode.This is known in those skilled in the art.
Positive electrode presoma of the present invention can by commercially available, also can oneself prepare.Its preparation method can be selected complex-precipitation method, spray drying process, collosol and gel etc.Above preparation method is known in those skilled in the art.Therefore not to repeat here for concrete preparation method.
Temperature when wherein, fusing initial temperature of the present invention refers to that material begins to melt.
High temperature inert swelling agent of the present invention also can be selected the material that meets above-mentioned condition or parameter by being purchased, for example Jiangsu day Shengji's art Industrial Co., Ltd. VII type expansion joint material.
Certainly the high temperature inert swelling agent also can oneself prepare.
High temperature inert swelling agent of the present invention is preferably composite material, and it forms by silicon rubber, polytetrafluoroethylene and alkali-free glass fibre are mixing.Mixing operation of holding office for those skilled in the art, therefore not to repeat here.
More preferably, the ratio of each component of high temperature inert swelling agent is: take the total weight of high temperature inert swelling agent as benchmark, silicon rubber accounts for 60～80wt%, and polytetrafluoroethylene accounts for 10～20wt%, and alkali-free glass fibre accounts for 10～20wt%.
Under the preferable case, the average grain diameter of positive electrode presoma of the present invention is 1～50 μ m, and the average grain diameter of high temperature inert swelling agent is for being 0.1～1mm; More preferably the positive electrode presoma is 3～25 μ m, and the high temperature inert swelling agent is 0.1～0.8mm.
Like this, on the one hand, be conducive to the high temperature inert expanding material to the abundant dispersion of positive electrode presoma, the agglomeration of positive electrode presoma when reducing high temperature.On the other hand, the separating of positive electrode and high temperature inert swelling agent after being conducive to sintering and finishing, because the very large great disparity of material particle size, directly sieving separating is simple.
The mass ratio of positive electrode presoma of the present invention and high temperature inert swelling agent is preferably 1: 0.1～and 1: 2; More preferably 1: 0.2～1: 0.5.
Wherein the lithium source also is known in those skilled in the art, is generally hydroxide or the lithium salts of lithium.Lithium of the present invention source is preferably in lithium hydroxide, lithium carbonate or the lithium nitrate one or more.
Under the preferable case, the addition in lithium of the present invention source and the mol ratio of positive electrode presoma are 1: 1.05～1: 1.2.
The positive electrode presoma is mixed with lithium source, high temperature inert swelling agent.Wherein, mixing can be adopted various common hybrid modes in this area, and for example ball milling mixes, and mixer mixes.The preferred ball milling of the present invention, more preferably wet ball-milling.
The concrete operations that mix are preferably: positive electrode presoma, lithium source and high temperature inert swelling agent are joined in the planetary ball mill, to wherein adding absolute ethyl alcohol, are ball milling 2～5h under 5～10rad/s at rotating speed again.
Then the material that mixes is sent in the sintering furnace high temperature sintering under oxygen-containing atmosphere.
The purpose of high temperature sintering is: at high temperature, positive electrode presoma and lithium source, oxygen reaction generate positive electrode.High temperature sintering of the present invention is preferably double sintering, is specially at 450～550 ℃ of lower constant temperature sintering 4～8h, then at 730～770 ℃ of lower constant temperature sintering 14～20h.
Oxygen-containing atmosphere of the present invention can be the mixed atmosphere of air atmosphere, pure oxygen atmosphere or oxygen and inert gas etc.
Partial pressure of oxygen under the preferred oxygen-containing atmosphere of the present invention is 0.03～0.1MPa.
From the material that sintering is finished, separate at last and remove the high temperature inert swelling agent, just obtained positive electrode.
Operation is removed in separation of the present invention can adopt several different methods, and the conventional granulates separation means can.The most direct simple method is to utilize the difference of material particle size, the removal high temperature inert of directly sieving swelling agent.
The invention will be further elaborated below in conjunction with specific embodiment.
Embodiment 1
Positive electrode presoma: Ni
0.8Co
0.2(OH)
2, average grain diameter is 15 μ m
The lithium source: lithium hydroxide, average grain diameter are 10 μ m
The high temperature inert swelling agent: Jiangsu day rises Science and Technology Ltd., model VII type expansion joint, its 700 ℃ lower with 25 ℃ under volume ratio be 3: 1, its average grain diameter is 0.5mm under the normal temperature
With 92.73Kg positive electrode presoma, 25.92kg lithium source, 24kg high temperature inert swelling agent joins in the planetary ball mill together, and to wherein adding the 80kg absolute ethyl alcohol, the control rotating speed is 5rad/s, ball milling 2.5h again.
The material that above-mentioned ball milling is complete is sent in the sintering furnace, passes into oxygen, keeps partial pressure of oxygen 0.06Pa.At 500 ℃ of lower constant temperature sintering 4h, and then at 750 ℃ of lower constant temperature sintering 16h.
Product cool to room temperature with sintering is finished utilizes screening method, and sieve removes the high temperature inert swelling agent.Obtain positive electrode and be denoted as A1.
Embodiment 2
As different from Example 1: its 700 ℃ of high temperature inert swelling agents lower with 25 ℃ under volume ratio be 2: 1, other parts are with embodiment 1.Obtain positive electrode and be denoted as A2.
Embodiment 3
As different from Example 1: the average grain diameter of positive electrode presoma is 5 μ m, and the average grain diameter of high temperature inert swelling agent is 0.3mm.Other parts are with embodiment 1.Obtain positive electrode and be denoted as A3.
Embodiment 4
As different from Example 1: the average grain diameter of positive electrode presoma is 40 μ m, and the average grain diameter of high temperature inert swelling agent is 0.8mm.Other parts are with embodiment 1.Obtain positive electrode and be denoted as A4.
Embodiment 5
Positive electrode presoma: Co
0.95Ti
0.05(OH)
2, average grain diameter is 15 μ m
Lithium source: lithium hydroxide, average grain diameter 10 μ m
The high temperature inert swelling agent: Jiangsu day rises Science and Technology Ltd., model VII type expansion joint, and its 700 ℃ volume ratios with 25 ℃ are 3: 1, average grain diameter is 0.5mm
With 92.73Kg positive electrode presoma, 25.92kg lithium source, 24kg high temperature inert swelling agent joins in the planetary ball mill together, and to wherein adding the 80kg absolute ethyl alcohol, the control rotating speed is 5rad/s, ball milling 2.5h again.
The material that above-mentioned ball milling is complete is sent in the sintering furnace, passes into oxygen, keeps partial pressure of oxygen 0.06Pa.At 500 ℃ of lower constant temperature sintering 4h, and then at 750 ℃ of lower constant temperature sintering 16h.
Product cool to room temperature with sintering is finished utilizes screening method, and sieve removes the high temperature inert swelling agent.Obtain positive electrode and be denoted as A5.
Comparative Examples 1
With embodiment 1 difference be: do not add the high temperature inert swelling agent.Other parts are with embodiment 1.Obtain positive electrode and be denoted as AC1.
Performance test:
The preparation of test battery:
(1) preparation of positive plate: positive electrode (A1-A5 and AC1), acetylene black and PVDF are dissolved in the 1-METHYLPYRROLIDONE as 100: 4: 5 take weight ratio, be coated on the aluminium foil after stirring, baking, temperature is 100 ± 5 ℃, rolling cut becomes positive plate to use tablet press machine to roll also.
(2) preparation of negative plate: graphite, acetylene black and PVDF are dissolved in the 1-METHYLPYRROLIDONE as 100: 3: 6 take weight ratio, are coated on the Copper Foil after stirring, baking, temperature is 100 ± 5 ℃, rolling cut becomes negative plate to use tablet press machine to roll also.
(3) polypropylene diaphragm that above-mentioned positive and negative electrode pole piece and 20 μ m are thick is wound into the rectangular lithium ion battery battery core, places in battery case and welds, and subsequently, injects 1.0mol/LLiPF
6/ (EC+EMC+DMC) (wherein EC, EMC and DMC mass ratio are 1: 1: 1) electrolyte is filled with, and test battery is made in sealing.
The specific capacity test:
At room temperature, test battery first with the 1.0mA constant current charge, by voltage 4.2V, at the 4.2V constant voltage charge, by electric current 0.1mA, is shelved 5min, with the 1.0mA constant-current discharge.Calculate its specific capacity, the results are shown in Table 1.
The cycle performance test:
At room temperature, first with the 0.8mA constant current charge, by voltage 4.2V, at the 4.2V constant voltage charge, by electric current 0.06mA, shelve 5min, with the 0.8mA constant-current discharge.Repeat 500 times, calculate 500 times capability retention.The results are shown in Table 1.
Table 1
| Specific capacity (mAh/g) | 500 capability retentions | |
| Embodiment 1 | 187 | 95％ |
| Embodiment 2 | 181 | 92％ |
| Embodiment 3 | 189 | 95％ |
| Embodiment 4 | 176 | 90％ |
| Embodiment 5 | 182 | 96％ |
| Comparative Examples 1 | 165 | 85％ |
As can be seen from Table 1: the relative Comparative Examples 1 of embodiment 1-5, the specific capacity of the positive electrode that it is prepared and 500 capability retentions have all had significantly raising.The preparation method of the present invention of this explanation can the Effective Raise positive electrode capacity and cycle performance.This explanation, preparation method of the present invention can eliminate the problem of anoxic, makes positive electrode presoma and oxygen reaction abundant.Thereby the overall performance of positive electrode is got a promotion.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the preparation method of a positive electrode, it comprises: the positive electrode presoma is mixed with lithium source, high temperature inert swelling agent, and then high temperature sintering under oxygen-containing atmosphere separates the high temperature inert swelling agent and removes;
The general formula of described positive electrode presoma is M
aX
b(OH)
2Wherein, 0.8≤a≤1,0≤b≤0.2, M is selected among Ni, Mn, the Co one or more, and X is metal-doped element, and X is selected from Fe, Al, Mg, Cr, Sr, Ti or the rare earth element one or more;
The fusing initial temperature of described high temperature inert swelling agent is greater than 800 ℃, and volume ratio is greater than 2 during its 700 ℃ of described high temperature inert swelling agents and 25 ℃ the time;
Wherein, to be that silicon rubber, polytetrafluoroethylene and alkali-free glass fibre are mixing form described high temperature inert swelling agent;
The average grain diameter of described positive electrode presoma is 1～50 μ m, and the average grain diameter of described high temperature inert swelling agent is 0.1～1mm;
Described high temperature sintering is included in 450～550 ℃ of lower constant temperature sintering 4～8h, then at 730～770 ℃ of lower constant temperature sintering 14～20h.
2. the preparation method of positive electrode according to claim 1 is characterized in that: take the total weight of high temperature inert swelling agent as benchmark, described silicon rubber accounts for 60～80wt%, and polytetrafluoroethylene accounts for 10～20wt%, and alkali-free glass fibre accounts for 10～20wt%.
3. the preparation method of positive electrode according to claim 1, it is characterized in that: the weight ratio of described positive electrode presoma and high temperature inert swelling agent is 1: 0.1～1: 2.
4. the preparation method of positive electrode according to claim 1 is characterized in that: the described wet ball grinding that is mixed into.
5. the preparation method of positive electrode according to claim 1 is characterized in that: described lithium source for in lithium hydroxide, lithium carbonate or the lithium nitrate one or more.
6. the preparation method of positive electrode according to claim 5, it is characterized in that: the mol ratio in described positive electrode presoma and lithium source is 1: 1.05～1: 1.2.
7. the preparation method of positive electrode according to claim 1, it is characterized in that: the partial pressure of oxygen of described oxygen-containing atmosphere is 0.03～0.1MPa.
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|---|---|---|---|
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|---|---|---|---|
| CN2010102188568A CN102315428B (en) | 2010-06-29 | 2010-06-29 | Preparation method for anode material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284756A (en) * | 1999-08-16 | 2001-02-21 | 复旦大学 | Active positive-pole material for lithium ion secondary cell and its preparation and use |
| US20050214645A1 (en) * | 2002-11-29 | 2005-09-29 | Seimi Chemical Co., Ltd. | Process for producing positive electrode active material for lithium secondary battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284756A (en) * | 1999-08-16 | 2001-02-21 | 复旦大学 | Active positive-pole material for lithium ion secondary cell and its preparation and use |
| US20050214645A1 (en) * | 2002-11-29 | 2005-09-29 | Seimi Chemical Co., Ltd. | Process for producing positive electrode active material for lithium secondary battery |
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