CN102225753B - Preparation method for lithium ion battery cathode materials - Google Patents
Preparation method for lithium ion battery cathode materials Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010406 cathode material Substances 0.000 title abstract 4
- 238000001354 calcination Methods 0.000 claims abstract description 124
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000010405 anode material Substances 0.000 claims description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000011164 primary particle Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000004137 mechanical activation Methods 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 62
- 229910010710 LiFePO Inorganic materials 0.000 description 28
- 239000002245 particle Substances 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229940062993 ferrous oxalate Drugs 0.000 description 6
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 description 6
- 238000003837 high-temperature calcination Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method for lithium ion battery cathode materials. Specifically, various synthesis methods like solid phase method and liquid phase method are adopted to prepare a precursor of lithium ion battery cathode materials such as LiFePO4. Then the precursor is subjected to joint calcination at a changing temperature. Thus, optimal design and control of the structure and appearance of the synthesized lithium ion battery cathode materials can be realized. Therefore, a preparation method for lithium ion battery electrode materials with high-rate and ultra high-rate charge-discharge performance is obtained.
Description
Technical field
The present invention relates to the preparation method of anode material for lithium-ion batteries, belong to the energy and material technical field, be specifically related to a kind ofly carry out alternating temperature by the presoma to the anode material for lithium-ion batteries that adopts the various synthetic methods preparations such as solid phase method, liquid phase method and unite calcining, reach optimal design and control to synthesis of anode material of lithium-ion battery structure and pattern, thereby acquisition has the preparation method of the lithium ion battery electrode material of high magnification and ultra-high magnifications charge-discharge characteristic.
Background technology
Lithium ion battery is the green secondary cell that grows up the nineties in 20th century, compare with secondary cells such as traditional plumbic acid, NI-G, ni-mhs, advantages such as lithium ion battery is high with its reversible capacity, good cycling stability, energy density are high, memory-less effect and enjoy favor are used widely on the small-sized movable power supply.Traditional anode material for lithium-ion batteries is mainly cobalt acid lithium (LiCoO
2), owing to containing noble metal, its price is more expensive, substantially account for the over half of lithium battery cost, and its limited capacity has also restricted lithium ion battery as the requirement with high-energy-density, long circulation life, green non-pollution and low-cost secondary power supply such as electric tool, electric motor car and hybrid electric vehicle.Thereby the Development of New Generation high-performance, green anode material for lithium-ion batteries is significant cheaply.
LiFePO4 (LiFePO
4) anode material for lithium-ion batteries has extended cycle life owing to having, security performance is good, raw material sources are abundant, cost is low, avirulence and the electric automobile etc. that advantage is considered to application prospect most such as fail safe is good be with one of dynamic lithium battery positive electrode, and obtained tentative application.But LiFePO
4The shortcoming that material electronics conductivity and ionic conductivity are low has restricted its charge-discharge performance under high magnification, thereby has hindered its scale on anode material for lithium-ion batteries to use.Common modified method mainly contains LiFePO at present
4The nanometer of material and porous, material with carbon-coated surface and doping etc.
Up to the present, usually carry out one-step calcination by the presoma to lithium ion anode material in the prior art and obtain positive electrode.This one-step calcination method is owing to being difficult to control simultaneously the structure factor that in synthetic material, the material high rate capability is played a crucial role, comprise high conductivity content mutually etc. in crystallinity, particle size and material, thereby the high rate capability of synthetic positive electrode can not get effective assurance.
Therefore, need the new technological measure of exploitation, realize the design of anode material for lithium-ion batteries structural optimization and control, make this material have good crystallinity, particle size is less and the high conductivity compound is appropriate advantage concurrently.
Summary of the invention
The invention provides a kind of method for preparing anode material for lithium-ion batteries, the method is united calcining by the presoma to the synthesis of anode material of lithium-ion battery that adopts solid phase method or Liquid preparation methods carries out step calcination under the different temperatures section alternating temperature, optimal design and the control of realization to synthetic this material structure and performance, have raising lithium ion anode material crystallinity concurrently, control its particle size, thereby obtain to have the anode material for lithium-ion batteries of high magnification and ultra-high magnifications charge-discharge characteristic.
Particularly, the preparation method of anode material for lithium-ion batteries provided by the invention comprises the following steps:
(1) provide the presoma of anode material for lithium-ion batteries;
(2) this presoma is carried out alternating temperature and unite calcining;
Wherein, described alternating temperature is united calcining and is comprised this presoma is implemented at least twice calcining in the temperature range of 300-900 ℃.
In one embodiment, the anode material for lithium-ion batteries for preparing by the inventive method is LiFePO
4Cell positive material.Uniting calcining by alternating temperature of the present invention has realized this LiFePO
4The optimal design of material structure and performance and control have also improved LiFePO
4The crystallinity of lithium ion anode material, control its particle size, original position is introduced the Fe of high conductivity simultaneously
2P and FeP.
Description of drawings
Fig. 1 is the resulting LiFePO of embodiment 1
4The stereoscan photograph of material.
Fig. 2 is the resulting LiFePO of embodiment 1
4The X-ray diffracting spectrum of material.
Fig. 3 is the resulting LiFePO of embodiment 1
4Discharge capacity under different multiplying.
Fig. 4 is for adopting the identical presoma of embodiment 1, and under identical atmosphere, respectively through (a) 600 ℃ of calcinings 20 hours, (b) 700 ℃ of calcinings are 4 hours, (c) 700 ℃ of calcinings 10 hours and (d) 800 ℃ of LiFePO that calcining obtained in 2 hours
4The SEM pattern of material.
Fig. 5 is for adopting the identical presoma of example 1, and under identical calcination atmosphere, respectively through (a) 600 ℃ of calcinings 20 hours, (b) 700 ℃ of calcinings are 4 hours, (c) 700 ℃ of calcinings 10 hours and (d) 800 ℃ of LiFePO that calcining obtained in 2 hours
4The discharge capacity of material under different discharge-rates.
Embodiment
The preparation method of anode material for lithium-ion batteries provided by the invention comprises that (1) provides the presoma of anode material for lithium-ion batteries; (2) this presoma is carried out alternating temperature and unite calcining, wherein, described alternating temperature is united calcining and is comprised this presoma is implemented at least twice calcination process in the temperature range of 300-900 ℃.
In preparation method of the present invention, the lithium ion anode material presoma the technology that can adopt any preparation lithium ion anode material presoma used in the art is provided.These technology include but not limited to: the various raw material source (such as source of iron, phosphorus source, lithium source and optional carbon source etc.) that will synthesize presoma in solid phase method is directly carried out the mechanical ball break-in and is become presoma under solid phase; Raw material are carried out the method for ball milling and process synthetic presoma through desolventizing in the liquid phase mediums such as distilled water, ethanol, acetone; The presoma that in liquid phase method, the methods such as sol-gel process, spray drying process, coprecipitation obtain, etc.
After the precursor of lithium ionic cell positive material oven dry that will obtain by above-mentioned any method, grinding, then unite calcining by alternating temperature, thereby form positive electrode.Implement alternating temperature and unite when calcining, directly under reducing atmosphere or inert atmosphere, carry out the substep alternating temperature of different time to making presoma and unite calcining in the temperature range of 300-900 ℃.
In a preferred embodiment, the substep alternating temperature of the present invention calcining step of uniting in calcining can carry out at twice.The temperature of calcining can be less than calcining heat for the second time for the first time, but the temperature of calcining also can be greater than calcining heat for the second time for the first time.
In one embodiment, alternating temperature of the present invention is united calcining and is comprised calcination process twice: at first at temperature lower calcination 0.5-25 hour of 300-750 ℃, calcined 0.5-15 hour under 600-900 ℃ more subsequently.
For example, can be at first 300～750 ℃, preferred 400～700 ℃, more preferably calcine for the first time in the shorter time period at the temperature of 500～650 ℃, for example calcination time is 0.5～25 hour, preferred 5～20 hours, more preferably 10～20 hours; Subsequently again 600-900 ℃, preferred 600～800 ℃, more preferably calcine for the second time under 650～750 ℃, calcination time is 1～20 hour, preferred 1～15 hour, more preferably 1～6 hour.Also can be first 600-900 ℃, preferred 600～800 ℃, more preferably calcine for the first time under 650～750 ℃, subsequently again 300～750 ℃, preferred 400～700 ℃, more preferably calcine for the second time at the temperature of 500～650 ℃.
In a preferred embodiment, for the first time 400～700 ℃ of calcinings 5～20 hours, then for the second time 600～800 ℃ of calcinings 1～15 hour.
In another preferred embodiment, for the first time 600～800 ℃ of calcinings 1～15 hour, then for the second time 400～700 ℃ of calcinings 5～20 hours.
In a preferred embodiment, for the first time 500～650 ℃ of calcinings 10～20 hours, then for the second time 650～750 ℃ of calcinings 1～6 hour.
In another preferred embodiment, for the first time 650～750 ℃ of calcinings 1～6 hour, then for the second time 500～650 ℃ of calcinings 10～20 hours.
Before the enforcement alternating temperature is united calcining, can also carry out presintering the temperature of 250～400 ℃ in inert atmosphere to the presoma that makes.Presintering is conducive to improve the final performance of material to a certain extent, and presintering is 1～10 hour usually.
The alternating temperature that carries out implementing after presintering is united calcining and can under reducing atmosphere or inert atmosphere, in the temperature range of 500-900 ℃, be carried out the substep alternating temperature of different time and unite calcining.
Can there is no the interval between each calcining step of step calcination, for example directly variations in temperature is arrived next step, but exist the interval there is no adverse influence between each step calcining yet.For example, can after first step calcining, material cooled be arrived room temperature, the second step calcining is carried out at the interval again after any long a period of time, as long as in interval procedure, deliquescence does not occur, this can realize by for example being placed in drier.
Calcination atmosphere can be the inert gases such as nitrogen or argon gas, can be also reducing atmosphere, as contains the mists such as the argon hydrogen of a small amount of hydrogen or nitrogen hydrogen.
In the methods of the invention, the source of iron that obtains presoma can be ferrous oxalate, ferric nitrate, ironic citrate, ferric phosphate etc., the phosphorus source can be ammonium dihydrogen phosphate, ferric phosphate etc., the lithium source can be lithium carbonate, lithium citrate, lithium hydroxide, lithium phosphate etc., and carbon source can be carbohydrate and the polymer such as polyvinyl alcohol (PVA) and polytetrafluoroethylene such as the acids such as alcohols, citric acid and laurate, sucrose and glucose such as ethylene glycol.
The inventor finds, at preparation LiFePO
4During anode material for lithium-ion batteries, if calcining for the first time generally need to enter calcining for the second time (being " high-temperature calcination " this moment) again for low temperature calcination (for example lower than 650 ℃ or lower than the temperature of calcining for the second time) after obtaining good crystallinity.If but calcining for the first time generally needs to generate a small amount of Fe for high-temperature calcination (for example higher than 650 ℃ or lower than the temperature of calcining for the second time)
2After P/FeP, then enter second step calcining (being low temperature calcination this moment).
In one embodiment, prepare LiFePO by the inventive method
4Anode material for lithium-ion batteries, the LiFePO that finally obtains
4The Fe that contains 1～15 % by weight in during anode material for lithium-ion batteries
2P/FeP.And Fe
2The content of P/FeP can be by alternating temperature being united calcining calcining heat and calcination time regulate and change.
The inventor also finds, when calcining was for low temperature calcination for the first time, the crystallinity of calcining can improve and improve by high-temperature calcination (calcining for the second time) process subsequently for the first time.When calcining as high-temperature calcination for the first time, even the synthetic Fe of calcining for the first time
2P/FeP, this high-temperature calcination may also can produce Fe to calcining for the second time (low temperature calcination) process
2P/FeP is favourable.
The LiFePO for preparing by the present invention
4The primary particle of material is of a size of nearly hundred nanometers to the hundreds of nanometer, mainly at 100nm～500nm.When there was reunion in primary particle, the size of agglomerated particle preferably was no more than 2 μ m.Because particle size is not several excessive tiny nanoscale degree to tens nanometers, thereby when the preparation electrode, the electrode preparation manipulation is easier to respect to several materials to tens nanometers, and is conducive to the higher compacted density of electrode acquisition.In addition, the LiFePO for preparing by the present invention
4Material granule also has good dispersiveness, with the LiFePO of existing method (as the one-step calcination method) acquisition in this area
4Material granule is compared, and the reunion degree of particle is less.
When using carbon source to prepare presoma, the LiFePO that preferably prepares by the inventive method
4The particle surface of material can realize that carbon coats by carbon source, thereby improves the surface conductivity of material, also plays the effect of controlling particle size simultaneously, can effectively improve LiFePO
4The dynamic performance of material and high rate performance.
When not using carbon source to prepare presoma, the LiFePO of the present invention's preparation
4Material can be substantially carbon-free LiFePO
4Material, its high magnification and ultra-high magnifications performance can be by the Fe of material situ generation
2P and FeP guarantee, for example original position generates the Fe of 1-15 % by weight, preferred 3.5～10 % by weight
2P and FeP.In addition, the LiFePO that does not have carbon coated
4Material has higher tap density, is conducive to LiFePO
4The raising of electrode volume capacity density.
Method applicability of the present invention is wide, need not introduce extras or reforming equipment, and calcine technology parameter adjustable extent is wide, can reach effective control and adjusting to structure and the particle size of anode material for lithium-ion batteries.Especially as synthetic LiFePO
4Material can obtain excellent high magnification and ultra-high magnifications charge-discharge performance as anode material for lithium-ion batteries,
Embodiment
The present invention may be better understood for following examples, but the present invention is not limited to following examples.
Embodiment 1
Take mol ratio as the ferrous oxalate of 1: 1: 1, ammonium dihydrogen phosphate, lithium hydroxide be as raw material, employing and metal cation mol ratio are that the ethylene glycol of 1: 1 is carbon source, above-mentioned original material is carried out the mechanical ball mill in ethanol medium on ball mill, Ball-milling Time is 4 hours.The ball milling product is stirred desolventizing and further dry in drying box under 80 ℃, after drying, powder body material carries out ball mill grinding again, and then in containing the argon hydrogen mixed atmosphere of a small amount of hydrogen, calcining is 20 hours under 600 ℃, then calcined again under 700 ℃ 4 hours, obtain containing a small amount of Fe
2The carbon of P coats LiFePO
4Material.Electro-chemical test shows, the capacity of resulting materials under 5C, 10C and 20C discharge-rate reaches and reach respectively 120,110 and 100mAh/g.
To the resulting LiFePO of embodiment 1
4Material scans with ESEM, and the photo that obtains is shown in Fig. 1.Demonstrate synthetic LiFePO in figure
4Has the more tiny particle size that is evenly distributed.The primary particle size is substantially below 500nm, and favorable dispersibility.The particle size of tiny dispersion is conducive to LiFePO
4Material obtains good high rate performance.
LiFePO resulting according to embodiment 1
4The X-ray diffracting spectrum of material is shown in Fig. 2.Demonstrate synthetic LiFePO in figure
4Good crystallinity, and contain micro-Fe
2P。LiFePO
4Good crystallinity and micro-high conductivity be Fe mutually
2The existence of P is conducive to improve LiFePO
4The high rate capability of material.
Embodiment 2
Take mol ratio as 1: 1: 1 ferrous oxalate, ammonium dihydrogen phosphate, lithium carbonate be as initial raw materials, above-mentioned raw material carried out mechanical ball milling in medium-acetone, Ball-milling Time is 3 hours.With the oven dry under 100 ℃ in drying box of ball milling product, then will dry afterproduct presintering 2 hours under 350 ℃ of conditions in nitrogen atmosphere.To the ball mill grinding of presintering product, then in containing the nitrogen and hydrogen mixture atmosphere of a small amount of hydrogen, calcining is 15 hours under 600 ℃, then calcines under 700 ℃ 5 hours again, obtains substantially carbon-free but contains a small amount of Fe
2The LiFePO of P and FeP
4Material.This material has good high magnification and ultra-high magnifications charge-discharge characteristic as anode material for lithium-ion batteries.
Take mol ratio as 1: 1: 1 ferrous oxalate, ammonium dihydrogen phosphate, lithium nitrate be as raw material, employing and metal cation mol ratio are that the citric acid of 1: 2 is that carbon source is carbon source, above-mentioned initial raw materials is dissolved in distilled water, adopt blender to stir under 80 ℃ until form gel, to the oven dry under 120 ℃ in drying box of this gel.Xerogel is mixed with appropriate conductive agent ball milling, then with this ball milling product in containing the argon hydrogen mixed atmosphere of a small amount of hydrogen, calcining is 16 hours under 600 ℃, and then calcining 2 hours under 750 ℃, synthesizes LiFePO
4Material.Resulting materials has good high magnification and ultra-high magnifications charge-discharge characteristic as lithium ion battery electrode material.
Embodiment 4
Take mol ratio as 1: 1: 1 ferrous oxalate, ammonium dihydrogen phosphate, lithium carbonate be as raw material, adopting with the metal cation mol ratio is that the ethylene glycol of 2: 1 is carbon source, above-mentioned raw material is carried out mechanical ball milling in ethanol medium, Ball-milling Time is 3 hours.Then to the ball milling product in drying box through 100 ℃ of oven dry.Again this ball milling product was calcined 20 hours under 550 ℃, and then in containing the nitrogen and hydrogen mixture atmosphere of a small amount of hydrogen through 750 ℃ of calcinings 2 hours, synthetic LiFePO
4Material.Gained LiFePO
4Material contains a small amount of carbon coated and Fe
2P, this material has good high magnification and ultra-high magnifications charge-discharge characteristic as lithium ion battery electrode material.
Embodiment 5
Take mol ratio as 1: 1: 1 ferrous oxalate, ammonium dihydrogen phosphate, lithium carbonate be as raw material, adopting with the metal cation mol ratio is that the ethylene glycol of 2: 1 is carbon source, above-mentioned raw material is carried out mechanical ball milling in ethanol medium, Ball-milling Time is 4 hours.Then to the ball milling product in drying box through 100 ℃ of oven dry.After should drying again the ball milling product in nitrogen atmosphere through 300 ℃ of presintering 5 hours, then in containing the nitrogen and hydrogen mixture atmosphere of a small amount of hydrogen through 750 ℃ of calcinings 2 hours, then calcining 12 hours under 600 ℃, synthetic LiFePO
4Material.Gained LiFePO
4Material contains a small amount of carbon coated and Fe
2P, this material has good high magnification and ultra-high magnifications charge-discharge characteristic as lithium ion battery electrode material.
Embodiment 6
Measure the LiFePO of embodiment 1
4The discharge capacity of material under different multiplying
2025 type simulated batteries are adopted in this test, take lithium as to electrode, and the LiPF take electrolyte as 1mol/L
6The mixed solution of ethylene carbonate EC/ dimethyl carbonate DMC (EC and DMC adopt the equal-volume ratio), barrier film adopts the Celgard2300 polypropylene porous film.LiFePO in positive electrode
4: graphite and acetylene black conductor: the ratio of PVDF binding agent is 75: 15: 10.Charging/discharging voltage scope 2.2-4.2V, the charging current under different discharge-rates is 0.1C (wherein 1C=170mA/g).
LiFePO
4Through the activation of the several circulations of preliminary examination, capacity reaches 165mAh/g to material under 0.1C, near its theoretical capacity.Its capacity under 1C, 5C, 10C and 20C discharge-rate reaches and reaches respectively 140,120,110 and 100mAh/g.Demonstrate material and have good high rate performance.This performance has benefited from LiFePO
4Material is tiny, evenly reach finely disseminated distribution of particles, good crystallinity and contain the Fe of micro-high conductivity
2P and FeP phase.
Comparative Examples
The acquisition of persursor material is identical with embodiment 1, and under identical atmosphere, respectively through (a) 600 ℃ calcining 20 hours, (b) 700 ℃ of calcinings are 4 hours, (c) 700 ℃ of calcinings 10 hours and (d) 800 ℃ of calcinings prepared LiFePO in 2 hours
4Material.
Above-mentioned material is scanned respectively with ESEM, the SEM pattern be shown in (a), (b), (c) of Fig. 4 and (d) in.Analyzing the SEM pattern can find out, through 600 ℃ of calcinings 20 hours and 700 ℃ of LiFePO that calcining obtained in 4 hours
4The reunion degree of material ((a) and (b)) is very large, the LiFePO that obtained in 2 hours through 800 ℃ of calcinings
4The particle size distribution of material (d) is very inhomogeneous, and the primary particle size is very large, and the part particle even substantially exceeds 2 μ m, and is larger after the part particle agglomeration, and this is unfavorable for that all material obtains good high rate capability.Through 700 ℃ of calcinings 10 hours (c) with first failed macroscopic obvious difference through 700 ℃ of materials of calcining 4 hours (embodiment 1) on the SEM pattern again through 600 ℃ of calcinings 20 hours, but learn the former Fe according to X diffraction Rietveld refine result
2P content is 2.5 % by weight, the latter's Fe
2P content is 4.3 % by weight.In particle size and under the condition that does not have obviously to distinguish that distributes, improve Fe
2P content is conducive to LiFePO from 2.5 % by weight to 4.3 % by weight
4Material obtains better high magnification and ultra-high magnifications charge-discharge performance.
Fig. 5 shows above-mentioned LiFePO
4Material (a), (b), (c) and (d) discharge capacity under different discharge-rates.Electrochemical test method as described in example 6 above.Comparison diagram 3 and Fig. 5 have illustrated and have adopted the synthetic LiFePO of associating alternating temperature calcining that puts down in writing in the present invention
4The chemical property of material is all much higher than adopting the synthetic capacity of one-step calcination under variant discharge-rate.
Following table has been summed up the performance parameter of embodiment 1 and Comparative Examples (a), (b), (c) and material (d)
Can clearly be seen that the LiFePO that obtains by the inventive method from above embodiment and table
4Anode material for lithium-ion batteries has effectively guaranteed the crystallinity of LiFePO4 by employing calcining of long period at relatively low temperature, and control its particle and have less size and good dispersiveness, the calcining of uniting the short period under high-temperature relatively, reach original position and introduce appropriate high conductivity Fe2P/FeP phase, and control again that particle size is not obvious grows up, thereby realized simultaneously good crystallinity, suitable particle size and good dispersed and suitable Fe
2The textural association of P/FeP content.Therefore, the LiFePO of the inventive method acquisition
4Anode material for lithium-ion batteries has been realized better charge-discharge power performance, high magnification and ultra-high magnifications performance, and is such as shown in Figure 5.
Claims (20)
1. the preparation method of an anode material for lithium-ion batteries comprises the following steps:
(1) provide the presoma of anode material for lithium-ion batteries;
(2) this presoma is carried out alternating temperature and unite calcining;
Wherein, described alternating temperature is united calcining and is comprised this presoma is implemented at least twice calcination process that carries out under different temperatures in the temperature range of 300-900 ℃,
Wherein, in described twice calcination process, the temperature of calcining is 300～750 ° of C for the first time, and the temperature of calcining is 600～900 ° of C for the second time; And
Wherein, the time of calcining is 0.5～25 hour for the first time, and the time of calcining is 0.5～15 hour for the second time.
2. according to claim 1 method, wherein, the temperature of calcining is 400～700 ° of C for the first time.
3. according to claim 2 method, wherein, the temperature of calcining is 500～650 ° of C for the first time.
4. according to claim 1 method, wherein, the temperature of calcining is 600～800 ° of C for the second time.
5. according to claim 4 method, wherein, the temperature of calcining is 650～750 ° of C for the second time.
6. according to claim 1 method, wherein, the time of calcining is 5～20 hours for the first time.
7. according to claim 1 method, wherein, the time of calcining is 1～15 hour for the second time.
8. the preparation method of an anode material for lithium-ion batteries comprises the following steps:
(1) provide the presoma of anode material for lithium-ion batteries;
(2) this presoma is carried out alternating temperature and unite calcining;
Wherein, described alternating temperature is united calcining and is comprised this presoma is implemented at least twice calcination process that carries out under different temperatures in the temperature range of 300-900 ℃,
Wherein, in described twice calcination process, the temperature of calcining is 900 ° of C of 600 – for the first time, and the temperature of calcining is 300～750 ° of C for the second time; And
Wherein, the time of calcining is 0.5～15 hour for the first time, and the time of calcining is 0.5～25 hour for the second time.
9. according to claim 8 method, wherein, the temperature of calcining is 600～800 ° of C for the first time.
10. according to claim 9 method, wherein, the temperature of calcining is 650～750 ° of C for the first time.
11. method according to claim 8, wherein, the temperature of calcining is 400～700 ° of C for the second time.
12. method according to claim 11, wherein, the temperature of calcining is 500～650 ° of C for the second time.
13. method according to claim 8, wherein, the time of calcining is 1～15 hour for the first time.
14. method according to claim 8, wherein, the time of calcining is 5～20 hours for the second time.
15. the method for any one according to claim 1～14, wherein, described alternating temperature is united calcining and is carried out in inert atmosphere or reducing atmosphere.
16. the method for any one according to claim 1～14 wherein, before alternating temperature associating calcining step, is carried out presintering in the temperature range of 250～400 ℃ to described presoma.
17. the method for any one according to claim 1～14, wherein, the described step that presoma is provided comprises provides source of iron, phosphorus source, lithium source and optional carbon source, then process by solid phase mechanical activation method, solid-state direct mechanical ball-milling method, sol-gal process or spray drying process, obtain thus presoma.
18. the method for any one according to claim 1～14, wherein said anode material for lithium-ion batteries are LiFePO
4Anode material for lithium-ion batteries.
19. the anode material for lithium-ion batteries of the method for any one preparation according to claim 1～18.
20. anode material for lithium-ion batteries according to claim 19, the average primary particle size of wherein said anode material for lithium-ion batteries is less than 500nm, and Fe
2P/FeP content is 3.5～10 % by weight.
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