CN102361071A - Preparation method for modified LiFePO4 lithium ion battery anode material - Google Patents
Preparation method for modified LiFePO4 lithium ion battery anode material Download PDFInfo
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- CN102361071A CN102361071A CN2011101752295A CN201110175229A CN102361071A CN 102361071 A CN102361071 A CN 102361071A CN 2011101752295 A CN2011101752295 A CN 2011101752295A CN 201110175229 A CN201110175229 A CN 201110175229A CN 102361071 A CN102361071 A CN 102361071A
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- ion battery
- lithium ion
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- lignin
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010405 anode material Substances 0.000 title claims abstract description 13
- 229910052493 LiFePO4 Inorganic materials 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 229920005610 lignin Polymers 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000003607 modifier Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 30
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000000498 ball milling Methods 0.000 claims description 19
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 239000000084 colloidal system Substances 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 13
- 238000000748 compression moulding Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 229910010710 LiFePO Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920005550 ammonium lignosulfonate Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229920001732 Lignosulfonate Polymers 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 34
- 239000002243 precursor Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract 2
- 229920003043 Cellulose fiber Polymers 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 14
- 229910000398 iron phosphate Inorganic materials 0.000 description 12
- -1 polypropylene Polymers 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000005456 alcohol based solvent Substances 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 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 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 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 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 239000008101 lactose Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000002881 soil fertilizer Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
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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 relates to a preparation method for a modified LiFePO4 lithium ion battery anode material, which belongs to the field of lithium ion battery materials. In the process of preparing a LiFePO4 lithium ion battery cathode material, a modifier is added, and the modifier is cellulose fiber, a lignin salt or a mixture of the two. According to the invention, cheap lignin, a renewable natural high-molecular material, is used as a carbon source precursor for the LiFePO4 lithium ion battery anode material, and lignin is widely available and easy to well mix with lithium source compounds, iron source compounds and phosphor source compounds once and for all; the prepared LiFePO4 lithium ion battery anode material has high purity and good electrochemical performance; a process for the anode material is simple and is easy to control; low production cost is obtained; a lithium ion battery made of the cathode material has a stable quality and 0.2C charge-discharge reversible specific capacity higher than 157 mAh/g, and battery capacity of the prepared lithium ion battery does not attenuate after 50 times of cycle; the method is applicable to large scale industrial production.
Description
Technical field
The invention belongs to the lithium ion battery material field, that be specifically related to is a kind of modification lithium-ion battery LiFePO
4Positive electrode.
Background technology
Characteristics such as lithium ion battery anode material lithium iron phosphate has that fail safe is good, cycle performance is excellent, environmental friendliness, raw material sources are extensive have become the emphasis of domestic and international industrialization.But the technology of preparing and the technological requirement of LiFePO4 are higher, extensive industrialization national less, and present only a few company has realized batch process, mainly is to have following problem in the preparation process of LiFePO4: (1) Fe
2+Be prone to be oxidized to Fe
3+(2) conductivity is low.These aspects have obtained important breakthrough in the recent period, work out many new technologies, have prepared well behaved LiFePO
4Positive electrode, as: (1) adopts inertia or reducing atmosphere to suppress Fe
2+Oxidation; (2) improve conductivity through adding modes such as conductive agent or doping.The LiFePO that wherein prepares the carbon containing conductive agent
4Positive electrode is the effective ways that improve its performance.Usually be employed in LiFePO at present
4Add organic substance in the precursor mixture as the carbon source precursor body, after heat treatment obtains LiFePO
4/ C composite material.The carbon source precursor body of having reported mainly comprises carbohydrates such as glucose, lactose, fructose, sucrose, polypropylene, polyethylene, polyvinyl alcohol etc., and the shortcoming that above-mentioned raw materials is done the carbon source precursor body is: price is higher relatively and be mostly non-renewable; With LiFePO
4Precursor material be difficult for mixing and cause unstable product quality; Need more repeatedly to grind and heat treatment, complicated process of preparation, product purity are not easy control.These all big limitations LiFePO
4The large-scale industrial production of/C anode material for lithium-ion batteries.
Lignin is the phenols natural polymers that occurring in nature content is only second to cellulosic complicacy, amorphism, three-dimensional netted space structure, extensively is present in the higher plant cell wall.The lignin wide material sources are main accessory substances of pulp and paper industry, also are indispensable accessory substances in the wood hydrolysis industry; Have renewable, cheap, degradability, performance such as nontoxic, pollution-free; Lignin is mainly used in rubber industry, plastics industry, polyurethane industrial in the existing industrial technology field; Binder is also as soil conditioner and fertilizer.
Summary of the invention
The object of the present invention is to provide a kind of rich raw material sources; Preparation technology is simple, be easy to control, and product purity height, steady quality, chemical property are good, and production cost is low; Low in the pollution of the environment, be suitable for the modification lithium-ion battery LiFePO of large-scale production
4The preparation method of positive electrode.
For realizing above-mentioned purpose, technical scheme of the present invention is: at lithium ion battery LiFePO
4Positive electrode prepares in the process, has added modifier: lignin fibre, lignin salt or their mixture.
Modification lithium-ion battery LiFePO of the present invention
4Positive electrode prepares process and may further comprise the steps:
Described modifier and Li source compound, Fe source compound and P source compound joined to react in the solvent to mix to generate contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture, described modifier accounts for 2～45% of Li source compound, Fe source compound and P source compound total weight; Under the protection of inert gas, carry out ball milling behind the vacuum drying; After the milled product compression moulding, obtain modification LiFePO through heat treatment
4Anode material for lithium-ion batteries.
One of optimized technical scheme of the present invention is: heat treatment mode is that the material with compression moulding was warming up to 350～450 ℃ of constant temperature calcinings 3～10 hours, is warming up to 650～800 ℃ of constant temperature calcinings again 5～20 hours, and cooling is cooled to room temperature then.
The preferred scheme of the present invention is: the speed of intensification is 5～30 ℃/min; The speed of cooling is 5～30 ℃/min.
One of optimized technical scheme of the present invention is: contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture be to stir through mixer to make it fully react, mix and obtain in 3-10 hour.Especially preferably adopt the double helix mixing and blending machine to stir.
One of optimized technical scheme of the present invention is: milled product is to be pressed into disk shape, cylindric, spherical, convex surface, concave surface or other various geometry moulding through the powder make-up machine.
One of optimized technical scheme of the present invention is: Li in Li source compound, Fe source compound, the P source compound: Fe: the P mol ratio is 1.0～1.3: 1.0: 1.0.
One of optimized technical scheme of the present invention is: what solvent adopted is deionized water or ethanol.
The preferred concrete preparation technology of the present invention, it comprises the steps:
The first step: preparation contains lithium, iron, the phosphorus solution of modifier: with deionized water or ethanol etc. as solvent; Li source compound, Fe source compound, P source compound and modifier are mixed in proportion; The Li of the lithium in its solution, iron, phosphorus: Fe: the P mol ratio is 1.0～1.3: 1.0: 1.0, the modifier addition was 2～45% of a mixture total weight amount, adopted the double helix mixing and blending machine; Stir and made it fully react, mix in 3-10 hour, generate and contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture, 45～90 ℃ of vacuum dryings then; Described modifier is lignin fibre, lignin salt or their mixture;
Second step: the material after will drying is put into the ball mill container ball milling 3～10 hours that fills hydrogen or nitrogen atmosphere;
The 3rd step: the material behind the ball milling is pressed into disk shape, cylindric, spherical, convex surface, concave surface or other various geometries through the powder make-up machine;
The 4th step: the material of compression moulding is incorporated with in the circular or square sintering vessel of lid;
The 5th step: the circular or square sintering vessel that will feed places rotary kiln sintered stove of atmosphere or channel-type kiln; In hydrogen or nitrogen atmosphere, heat up with 5～30 ℃/min rate of heat addition, in 350～450 ℃ of constant temperature calcinings 3～10 hours; 5～30 ℃/min rate of heat addition heats up again; In 650～800 ℃ of constant temperature calcinings 5～20 hours, be cooled to room temperature with 5～30 ℃/min cooling rate then, make modification lithium-ion battery LiFePO
4Positive electrode.
In the such scheme of the present invention: Li source compound can be selected from lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate or lithium phosphate etc.Fe source compound is selected from ferric oxalate, ferric phosphate, di-iron trioxide or tri-iron tetroxide etc.P source compound is selected from ammonium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium phosphate or ferric phosphate.Inert gas can be nitrogen or argon gas.
In the such scheme of the present invention: lignin salt is one or more in ammonium lignosulphonate, sodium lignin sulfonate, calcium lignosulfonate, the magnesium lignosulfonate.
Propose with lignin composition modification lithium-ion battery LiFePO by the present invention
4The preparation method of positive electrode, raw material sources are abundant, and chemical property is good, and production cost is low, and 0.2C charges and discharge reversible specific capacity up to 157mAh/g, through 50 not decay of cycle battery capacity.
Modification LiFePO of the present invention
4The preparation method of anode material for lithium-ion batteries has following distinguishing feature:
(1) the present invention uses the cheap renewable natural macromolecular material of lignin as LiFePO
4The modifier of anode material for lithium-ion batteries, with material modified comparing such as carbohydrates such as glucose, lactose, fructose, sucrose, polypropylene, polyethylene, polyvinyl alcohol, raw material sources are abundant, material settling out, inexpensive, sustainable providing.In addition; It is a kind of many rings macromolecule organic that contains many negative electricity group that the present invention adopts the modifier lignin; The huge surface area of self particle makes it that very strong adsorption capacity arranged, to stronger affinity being arranged like Fe, Li, P etc., and can be as the good carrier of various particles; In addition, its three-dimensional build microstructure also is beneficial to the absorption of various particles; Dispersiveness that it is good and surface activity can be used for the dispersant of abrasive process, and this is beneficial to LiFePO
4The mixing of precursor material, the lignin RESEARCH OF PYROCARBON can suppress LiFePO
4The growth of crystal grain improves LiFePO
4Electronic conductivity, and can original position in sintering process generate reducing atmosphere and suppress Fe
2+Advantages such as oxidation.Therefore, the inventor proposes with lignin modification lithium ion battery LiFePO
4Positive electrode; Contain many rings macromolecule organic of many negative electricity group through lignin, metal ion is had stronger affinity, microstructure is three-dimensional netted space structure; Uneven and porous; Infall is flat, and good toughness, dispersiveness and chemical stability are arranged, and is easy to disposable and Li source compound, Fe source compound and P source compound and mixes lithium ion battery LiFePO
4Positive electrode carries out modification.
(2) through lignin modification, improved LiFePO
4Electronic conductivity, reduced LiFePO
4Polarization, increased LiFePO
4The charge-discharge performance of positive electrode; Lignin is arranged again in heat treatment process, gas can at the uniform velocity spread, and makes solid phase reaction more even.
(3) the lignin modification agent has suppressed LiFePO
4The growth of crystal grain has increased LiFePO
4Specific area, make LiFePO
4Material can fully contact with electrolyte, has compensated Li
+Deviate from/charge balance in the telescopiny, and then improve LiFePO
4Chemical property.
The present invention's advantage further also comprises: the material behind the ball milling is pressed into disk shape, cylindric, spherical, convex surface, concave surface or other various geometries, accelerates the solid-phase sintering reaction, shorten the reaction time, energy savings.
The control of protection gas and sintering temperature can make guarantees Fe
2+Not oxidized and LiFePO 4 material crystallization.
In addition, stir through sufficient the mixing in earlier stage in technology, make Li source compound, Fe source compound, P source compound and lignin modification agent raw material in the ethanol equal solvent, fully reaction, mixing generate and contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture, realized that really phosphorus, iron, lithium dimer level level mix, the mixture homogeneity of raw material is greatly improved, reach the degree that mixes of ionic level.
The method of synthesizing iron lithium phosphate of the present invention, prescription is simple, and raw material is merely elements such as hydrocarbon oxygen nitrogen, is easy in the high-temperature process remove, and gained LiFePO4 product purity is high, chemical property is good.Next adopts the powder compacting sintering process to shorten the reaction time, energy savings, and production cost is low, and the favorable reproducibility of different batches product is prone to realize the commercial scale cleaner production, and three-waste free discharge is suitable for large-scale industrial production.
Description of drawings
Fig. 1 is the stereoscan photograph of iron phosphate powder, and the product particle size has the agglomeration of particle basically less than 3 microns.
Fig. 2 is an X-ray diffractogram, and the iron phosphate powder of analyzing gained is pure olivine-type rhombic system phase structure.
Fig. 3 is that the battery that makes of the positive electrode by embodiment 1 is with the 0.2C charging and discharging curve.
Fig. 4 is that the battery that the positive electrode by embodiment 1 makes shows through 50 not decay of cycle battery capacity.
Embodiment
Following embodiment is intended to explain the present invention rather than to further qualification of the present invention.
Embodiment 1
Add 73.82 gram alcohol solvents at the double helix mixing and blending machine; Add 40.63 gram lithium carbonates, 179.89 gram ferrous oxalates, 115.03 gram ammonium dihydrogen phosphates and 33.55 gram ammonium lignosulphonates while stirring one by one; Continue to stir 7 hours to fully reacting, mixing, generate and contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture, 60 ℃ of vacuum dryings then; Dried material is put into the ball mill container ball milling 5 hours that fills hydrogen or nitrogen atmosphere; Material behind the ball milling is pressed into the disk shape through the powder make-up machine, and the material of compression moulding places the rotary kiln sintered stove of atmosphere, in hydrogen or nitrogen atmosphere; Heat up with the 10 ℃/min rate of heat addition; In 400 ℃ of constant temperature calcinings 5 hours, the 10 ℃/min rate of heat addition heated up again, in 680 ℃ of constant temperature calcinings 12 hours; Be cooled to room temperature with 10 ℃/min cooling rate then, make iron phosphate powder or doped iron lithium phosphate powder.
Fig. 1 is the stereoscan photograph of iron phosphate powder, and the product particle size has the agglomeration of particle basically less than 3 microns.Fig. 2 is an X-ray diffractogram, and the iron phosphate powder of analyzing gained is pure olivine-type rhombic system phase structure.
Getting the above-mentioned iron phosphate powder that makes is positive active material, and acetylene black is conductive agent, and Kynoar (PVDF) is a binding agent; By mass ratio is mixing in 85: 10: 5, adds an amount of N-methyl pyrrolidone (NMP) and stirs, and coats and processes positive plate on the aluminium foil; 80 ℃ of vacuumize 8h in vacuum drying chamber; As negative pole, microporous polypropylene membrane (Celgard 2400) is as barrier film with metal lithium sheet, 1mol/L LiPF
6The mixed solution of (EC: DMC=1: 1, volume ratio) is an electrolyte, in the glove box of applying argon gas, is assembled into button cell.Carry out the charge and discharge cycles test with the battery controlled testing instrument, voltage range is 2.0～3.7V.Fig. 3 is with the 0.2C charging and discharging curve, can be known by Fig. 3, and the reversible specific capacity of gained LiFePO4 is up to 157mAh/g, and Fig. 4 shows through 50 not decay of cycle battery capacity.
Embodiment 2
Add 75.03 gram alcohol solvents at the double helix mixing and blending machine; Add 46.15 gram lithium hydroxides, 179.89 gram ferrous oxalates, 115.03 gram ammonium dihydrogen phosphates and 34.11 gram ammonium lignosulphonates while stirring one by one; Continue to stir 7 hours to fully reacting, mixing, generate and contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture, 60 ℃ of vacuum dryings then; Dried material is put into the ball mill container ball milling 5 hours that fills hydrogen or nitrogen atmosphere; Material behind the ball milling is pressed into the disk shape through the powder make-up machine, and the material of compression moulding places the rotary kiln sintered stove of atmosphere, in hydrogen or nitrogen atmosphere; Heat up with the 10 ℃/min rate of heat addition; In 400 ℃ of constant temperature calcinings 5 hours, the 10 ℃/min rate of heat addition heated up again, in 680 ℃ of constant temperature calcinings 12 hours; Be cooled to room temperature with 10 ℃/min cooling rate then, make iron phosphate powder or doped iron lithium phosphate powder.Method by execution mode 1 is assembled into button cell, and with the 0.2C rate charge-discharge, the specific discharge capacity of sample is 155mAh/g.
Embodiment 3
Add 77.21 gram alcohol solvents at the double helix mixing and blending machine; Add 56.03 gram lithium oxalates, 179.89 gram ferrous oxalates, 115.03 gram ammonium dihydrogen phosphates and 35.09 gram ammonium lignosulphonates while stirring one by one; Continue to stir 7 hours to fully reacting, mixing, generate and contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture, 60 ℃ of vacuum dryings then; Dried material is put into the ball mill container ball milling 5 hours that fills hydrogen or nitrogen atmosphere; Material behind the ball milling is pressed into the disk shape through the powder make-up machine, and the material of compression moulding places the rotary kiln sintered stove of atmosphere, in hydrogen or nitrogen atmosphere; Heat up with the 10 ℃/min rate of heat addition; In 400 ℃ of constant temperature calcinings 5 hours, the 10 ℃/min rate of heat addition heated up again, in 680 ℃ of constant temperature calcinings 12 hours; Be cooled to room temperature with 10 ℃/min cooling rate then, make iron phosphate powder or doped iron lithium phosphate powder.Method by execution mode 1 is assembled into button cell, and with the 0.2C rate charge-discharge, the specific discharge capacity of sample is 153mAh/g.
Embodiment 4
Add 73.82 gram alcohol solvents at the double helix mixing and blending machine; Add 40.63 gram lithium carbonates, 179.89 gram ferrous oxalates, 115.03 gram ammonium dihydrogen phosphates and 33.55 gram sodium lignin sulfonates while stirring one by one; Continue to stir extremely fully reaction in 7 hours, mix, generate and contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture, 60 ℃ of vacuum dryings then; Dried material is put into the ball mill container ball milling 5 hours that fills hydrogen or nitrogen atmosphere; Material behind the ball milling is pressed into the disk shape through the powder make-up machine, and the material of compression moulding places the rotary kiln sintered stove of atmosphere, in hydrogen or nitrogen atmosphere; Heat up with the 10 ℃/min rate of heat addition; In 400 ℃ of constant temperature calcinings 5 hours, the 10 ℃/min rate of heat addition heated up again, in 680 ℃ of constant temperature calcinings 12 hours; Be cooled to room temperature with 10 ℃/min cooling rate then, make iron phosphate powder or doped iron lithium phosphate powder.Method by execution mode 1 is assembled into button cell, and with the 0.2C rate charge-discharge, the specific discharge capacity of sample is 147mAh/g.
Add 73.82 gram alcohol solvents at the double helix mixing and blending machine; Add 40.63 gram lithium carbonates, 179.89 gram ferrous oxalates, 115.03 gram ammonium dihydrogen phosphates and 33.55 gram calcium lignosulfonates while stirring one by one; Continue to stir extremely fully reaction in 7 hours, mix, generate and contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture, 60 ℃ of vacuum dryings then; Dried material is put into the ball mill container ball milling 5 hours that fills hydrogen or nitrogen atmosphere; Material behind the ball milling is pressed into the disk shape through the powder make-up machine, and the material of compression moulding places the rotary kiln sintered stove of atmosphere, in hydrogen or nitrogen atmosphere; Heat up with the 10 ℃/min rate of heat addition; In 400 ℃ of constant temperature calcinings 5 hours, the 10 ℃/min rate of heat addition heated up again, in 680 ℃ of constant temperature calcinings 12 hours; Be cooled to room temperature with 10 ℃/min cooling rate then, make iron phosphate powder or doped iron lithium phosphate powder.Method by execution mode 1 is assembled into button cell, and with the 0.2C rate charge-discharge, the specific discharge capacity of sample is 145mAh/g.
Embodiment 6
Add 73.82 gram alcohol solvents at the double helix mixing and blending machine; Add 40.63 gram lithium carbonates, 179.89 gram ferrous oxalates, 115.03 gram ammonium dihydrogen phosphates and 33.55 gram magnesium lignosulfonates while stirring one by one; Continue to stir extremely fully reaction in 7 hours, mix, generate and contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture, 60 ℃ of vacuum dryings then; Dried material is put into the ball mill container ball milling 5 hours that fills hydrogen or nitrogen atmosphere; Material behind the ball milling is pressed into the disk shape through the powder make-up machine, and the material of compression moulding places the rotary kiln sintered stove of atmosphere, in hydrogen or nitrogen atmosphere; Heat up with the 10 ℃/min rate of heat addition; In 400 ℃ of constant temperature calcinings 5 hours, the 10 ℃/min rate of heat addition heated up again, in 680 ℃ of constant temperature calcinings 12 hours; Be cooled to room temperature with 10 ℃/min cooling rate then, make iron phosphate powder or doped iron lithium phosphate powder.Method by execution mode 1 is assembled into button cell, and with the 0.2C rate charge-discharge, the specific discharge capacity of sample is 152mAh/g.
Embodiment 7
Add 73.82 gram alcohol solvents at the double helix mixing and blending machine; Add 40.63 gram lithium carbonates, 179.89 gram ferrous oxalates, 115.03 gram ammonium dihydrogen phosphates and 33.55 gram lignin fibres while stirring one by one; Continue to stir fully reaction in 7 hours, mix, generate and contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture, 60 ℃ of vacuum dryings then; Dried material is put into the ball mill container ball milling 5 hours that fills hydrogen or nitrogen atmosphere; Material behind the ball milling is pressed into the disk shape through the powder make-up machine, and the material of compression moulding places the rotary kiln sintered stove of atmosphere, in hydrogen or nitrogen atmosphere; Heat up with the 10 ℃/min rate of heat addition; In 400 ℃ of constant temperature calcinings 5 hours, the 10 ℃/min rate of heat addition heated up again, in 680 ℃ of constant temperature calcinings 12 hours; Be cooled to room temperature with 10 ℃/min cooling rate then, make iron phosphate powder or doped iron lithium phosphate powder.Method by execution mode 1 is assembled into button cell, and with the 0.2C rate charge-discharge, the specific discharge capacity of sample is 148mAh/g.
Claims (8)
1. modification LiFePO
4The preparation method of anode material for lithium-ion batteries is characterized in that, at lithium ion battery LiFePO
4Positive electrode prepares in the process, has added modifier: lignin fibre, lignin salt or their mixture.
2. preparation method according to claim 1 is characterized in that, at lithium ion battery LiFePO
4Positive electrode prepares in the process, described modifier and Li source compound, Fe source compound and P source compound is joined to react in the solvent to mix to generate contain Fe
2+, PO
4 3-, Li
+The liquid phase colloid admixture, described modifier accounts for 2～45% of Li source compound, Fe source compound and P source compound total weight; Under the protection of inert gas, carry out ball milling behind the vacuum drying; After the milled product compression moulding, obtain modification LiFePO through heat treatment
4Anode material for lithium-ion batteries.
3. preparation method according to claim 2; It is characterized in that; Described heat treatment mode is that the material with compression moulding was warming up to 350～450 ℃ of constant temperature calcinings 3～10 hours, is warming up to 650～800 ℃ of constant temperature calcinings again 5～20 hours, and cooling rate is cooled to room temperature then.
4. preparation method according to claim 3 is characterized in that, the speed of intensification is that the speed of 5～30 ℃/min cooling is 5～30 ℃/min.
5. preparation method according to claim 2 is characterized in that, the described Fe that contains
2+, PO
4 3-, Li
+The liquid phase colloid admixture be to stir through mixer to make it fully react, mix and obtain in 3-10 hour.
6. preparation method according to claim 2 is characterized in that, described milled product is to be pressed into disk shape, cylindric, spherical, convex, spill or other various geometry moulding through the powder make-up machine.
7. preparation method according to claim 2 is characterized in that, Li in Li source compound, Fe source compound, the P source compound: Fe: the P mol ratio is 1.0～1.3: 1.0: 1.0.
8. according to each described method of claim 1-6, it is characterized in that described lignin salt is selected from ammonium lignosulphonate, sodium lignin sulfonate, calcium lignosulfonate, the magnesium lignosulfonate one or more.
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| CN103887493A (en) * | 2014-02-24 | 2014-06-25 | 杭州电子科技大学 | Anode material for lithium ion battery and preparation method of anode material |
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| CN107403932A (en) * | 2016-05-20 | 2017-11-28 | 苏州宝时得电动工具有限公司 | Positive electrode for battery, its preparation method and the battery with the positive pole |
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| CN106207173B (en) * | 2016-08-31 | 2018-07-10 | 山东精工电子科技有限公司 | A kind of method that lithium iron phosphate positive material is prepared based on colloid skeleton |
| CN108390043A (en) * | 2018-03-07 | 2018-08-10 | 齐鲁工业大学 | A kind of sodium-ion battery positive material Na3V2(PO4)3/ C and preparation method thereof |
| CN108390043B (en) * | 2018-03-07 | 2020-06-19 | 齐鲁工业大学 | A kind of sodium ion battery cathode material Na3V2(PO4)3/C and preparation method thereof |
| JP2020102322A (en) * | 2018-12-20 | 2020-07-02 | 太平洋セメント株式会社 | Positive electrode active material for secondary battery, and method for producing the same |
| JP7158269B2 (en) | 2018-12-20 | 2022-10-21 | 太平洋セメント株式会社 | Positive electrode active material for secondary battery and method for producing the same |
| CN111392706A (en) * | 2020-03-23 | 2020-07-10 | 广东光华科技股份有限公司 | Method for recycling waste lithium iron phosphate anode material |
| CN111392706B (en) * | 2020-03-23 | 2021-11-23 | 广东光华科技股份有限公司 | Method for recycling waste lithium iron phosphate anode material |
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