CN102456882A - Lithium-ion battery cathode material and preparation method thereof - Google Patents
Lithium-ion battery cathode material and preparation method thereof Download PDFInfo
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- CN102456882A CN102456882A CN2010105238681A CN201010523868A CN102456882A CN 102456882 A CN102456882 A CN 102456882A CN 2010105238681 A CN2010105238681 A CN 2010105238681A CN 201010523868 A CN201010523868 A CN 201010523868A CN 102456882 A CN102456882 A CN 102456882A
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- lithium
- positive electrode
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 239000010406 cathode material Substances 0.000 title abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 37
- 239000010936 titanium Substances 0.000 claims description 37
- 239000007774 positive electrode material Substances 0.000 claims description 24
- 239000011651 chromium Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 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 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 229940117975 chromium trioxide Drugs 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 150000003891 oxalate salts Chemical class 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 8
- 239000006182 cathode active material Substances 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 12
- 239000011149 active material Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910015868 MSiO Inorganic materials 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000011160 research Methods 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- DOCYQLFVSIEPAG-UHFFFAOYSA-N [Mn].[Fe].[Li] Chemical class [Mn].[Fe].[Li] DOCYQLFVSIEPAG-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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 provides a lithium-ion battery cathode material. The cathode material comprises a cathode active material. The structural formula of the cathode active material is Li2+xMSi1-xNxO4, wherein M is selected from Mn, Fe or Mn1-yFey, N is selected from Ti, Cr or Ti1-zCrz, 0.01<x<=0.5, 0<y<1, and 0<z<1. Meanwhile, the invention also provides a preparation method of the cathode material. The preparation method has simple process, and the prepared cathode material has excellent performances, stable structure, higher specific capacity and coulombic efficiency, better cycle performance and excellent high-rate charge/discharge property.
Description
Technical field
The present invention relates to the lithium ion battery field, in particular, relate to positive electrode of a kind of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery is since last century, the nineties was come out; Because it has high-energy-density; High power density and excellent cycle performance; Being widely used in fields such as mobile communication, notebook computer, video camera, camera, portable instrument, also is the electric automobile studied energetically of various countries, the first-selected supporting power supply of space power system, becomes the first-selection of the alternative energy.
Anode material for lithium-ion batteries is one of critical material of decision lithium ion battery performance, also is the focus and the difficult point of prior art research, and existing general commercial positive electrode is LiCoO
2But, and have certain toxicity and can pollute environment because the rareness of cobalt resource causes the battery production cost too high; Particularly this metal oxide cathode material is strong oxidizer when Charging state, directly contacts with the organic electrolyte of present use to have serious potential safety hazard; Another kind of common positive electrode LiMn
2O
4Though with low cost and environmentally friendly, the cycle performance of this kind material is relatively poor, Mn
2+Stripping also can cause certain safety problem; Therefore seeking new material is the focus that this area is generally studied.
Since 1997, research groups such as John B Goodenough reported LiMPO
4(M=Fe, Mn, Co, anode material for lithium-ion batteries Ni), yet LiFePO
4The electronic conductivity and the energy density of material are lower, are difficult to satisfy the needs of high-capacity lithium-ion secondary cell of new generation.
2005, Anton Nyten adopted solid phase method to synthesize Li
2FeSiO
4Material; 2006, R. Dominko and research group thereof adopted improved sol-gal process to synthesize Li first
2MnSiO
4Positive electrode has obtained comparatively desirable chemical property; Li
2MSiO
4(M=Fe, Mn) all belongs to rhombic system, and space group is Pmn21, with Li
3PO
4Low temperature structure similar, Li, Si, Fe (Mn) are filled in the tetrahedron space of O atom, and alternately arrange.Because anodal this material of silicate system has characteristics such as cost of material is low, environmentally friendly, security performance excellence, and Li
2MSiO
4It is higher that (M=Fe, Mn) material also has theoretical specific capacity, and operating voltage is than advantages such as height, thereby, be considered to have very much the anode material for lithium-ion batteries of application potential.
Yet disclosed silicate is positive electrode in the prior art, for example: Li
2FeSiO
4, Li
2MnSiO
4And Li
2VOSiO
4Though have higher specific capacity; But all owing to the poor electric conductivity of silicate material; Electronic conductivity and ionic conductivity are lower, cause the high rate charge-discharge poor performance of material, can not be applicable to the needs of the high-capacity lithium-ion secondary cell of high rate charge-discharge.
Summary of the invention
The present invention is in order to solve the poor electric conductivity that silicate of the prior art is positive electrode, the unfavorable problem of high rate charge-discharge performance.
In view of the above, the present invention provides a kind of positive electrode of lithium ion battery, and said positive electrode comprises positive electrode active materials, and the structural formula of said positive electrode active materials is Li
2+xMSi
1-xN
xO
4, wherein, M is selected from Mn, Fe or Mn
1-yFe
y, N is selected from Ti, Cr or Ti
1-zCr
z, 0.01＜x≤0.5,0＜y＜1,0＜z＜1.
Inventor of the present invention adopts the positive electrode active materials of said structure to have higher high rate charge-discharge performance through discovering, reason possibly be Ti or Cr doped and substituted lithium iron manganese silicate (Li originally
2MSiO
4M is Fe, Mn) part silicon position in the structure; And make the positive electrode active materials of said structure can introduce the tetrahedron space that X lithium ion occupies oxygen atom more; Promptly in the process of battery charging and discharging, the positive electrode active materials with said structure can be deviate from more lithium ion, thereby obtains higher specific discharge capacity; Simultaneously, the doping of Ti or Cr has reduced the energy when lithium ion takes off embedding, improves the diffusion coefficient of lithium ion in positive electrode, thereby improves the high rate charge-discharge performance of material greatly.
In described positive electrode, said M is Mn
1-yFe
y, N is Ti, 0.1≤x≤0.5,0.5≤y＜1.
In described positive electrode, the surface of said positive electrode active materials also is coated with material with carbon element, and in said positive electrode, the content of said positive electrode active materials is 85wt%-95 wt %, and the content of said material with carbon element is 5wt%-15 wt %.
Simultaneously, the present invention also provides the preparation method of above-mentioned positive electrode, comprises the steps:
Step 1, with lithium source, M source, silicon source, N source mixing and ball milling, obtain mixed-powder;
Step 2, above-mentioned mixed-powder is heat-treated under inert atmosphere, obtaining structural formula is Li
2+xMSi
1-xN
xO
4Product, wherein, M is selected from Mn, Fe or Mn
1-yFe
y, N is selected from Ti, Cr or Ti
1-zCr
z, this scope with claim of 0.01＜x≤0.5 seems different, 0＜y＜1,0＜z＜1.
In described preparation method, the mol ratio of the Li:M:Si:N in said lithium source, M source, silicon source, the N source is (2-2.5): 1: (1-0.5): (0.01-0.5).
In described preparation method, said lithium source is selected from one or more in lithium carbonate, lithium oxalate, lithium acetate, lithium hydroxide, lithium chloride, lithium nitrate or the lithium fluoride; Said M source is selected from one or more in carbonate, oxalates, acetate, nitrate, chloride or the oxide of M; Said N source is selected from the chloride of N or in the oxide one or more; Said silicon source is selected from one or more in nano silicon, aerosil, methyl silicate, tetraethoxysilane, Ludox, positive silicic acid or the silica gel.
In described preparation method, said M source is selected from least a in manganese acetate, manganese carbonate, manganese nitrate, manganese oxalate, ferrous oxalate, frerrous chloride, the ferrous nitrate, and said N source is selected from least a in titanium dioxide, the chromium trioxide.
In described preparation method, the medium of said ball milling is an absolute ethyl alcohol.
In described preparation method, in step 1, also be added with the carbon source mixing and ball milling, said carbon source is selected from one or more in sucrose, glucose, citric acid, ethylene glycol, the polyvinyl alcohol.
In described preparation method, said inert atmosphere is the mist of argon gas or argon gas and hydrogen; Said heat treated temperature is 650-850 ℃, and the time is 8-20 hour.
Preparation method's of the present invention technology is simple, the excellent performance of the positive electrode for preparing, and Stability Analysis of Structures has higher specific capacity, enclosed pasture efficient and better cycle performance, and has excellent high rate charge-discharge performance; Secondly, the positive electrode for preparing is nano-particle material, the particle size distribution homogeneous of material, particle diameter are distributed between the 50-100 nanometer, crystalline form is perfect.
Description of drawings
Fig. 1 is the Li of the embodiment of the invention 1 preparation
2Mn
0.5Fe
0.5Si
0.5Ti
0.5O
4XRD figure.
Fig. 2 is the Li of the embodiment of the invention 1 preparation
2Mn
0.5Fe
0.5Si
0.5Ti
0.5O
4FESEM figure.
Fig. 3 is the Li of the embodiment of the invention 1 preparation
2Mn
0.5Fe
0.5Si
0.5Ti
0.5O
4The first time discharge and recharge and the curve chart that discharges and recharges for the second time.
Embodiment
Clearer for technical problem, technical scheme and beneficial effect that the present invention is solved, below in conjunction with accompanying drawing and embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The present invention provides a kind of positive electrode with excellent high rate charge-discharge performance, and said positive electrode comprises positive electrode active materials, and the structural formula of said positive electrode active materials is Li
2+xMSi
1-xN
xO
4, wherein, M is selected from Mn, Fe or Mn
1-yFe
y, N is selected from Ti, Cr or Ti
1-zCr
z, this scope with claim of 0.01＜x≤0.5 seems different, 0＜y＜1,0＜z＜1.Capacity height, enclosed pasture efficient height, high rate charge-discharge performance with positive electrode of said structure are good.
Lithium ion in the said structure can excessive stable existence, reason possibly be Ti or Cr doped and substituted lithium iron manganese silicate structure (Li originally
2MSiO
4M=Fe, Mn) in part silicon position; And make the positive electrode active materials of said structure can introduce the tetrahedron space that X lithium ion occupies oxygen atom more; Promptly in the process of battery charging and discharging, the positive electrode active materials with said structure can be deviate from more lithium ion, thereby obtains higher specific discharge capacity; Simultaneously, the doping of Ti or Cr has reduced the energy when lithium ion takes off embedding, improves the diffusion coefficient of lithium ion in positive electrode, thereby can greatly improve the high rate charge-discharge performance of material.And this material is a rhombic system, Pmn2
1Space group can be taken off embedding at a axle, carries out three-dimensional diffusion simultaneously, Stability Analysis of Structures, and it is flexible that lithium ion takes off embedding.
At Li of the present invention
2+xMSi
1-xN
xO
4In the positive electrode active materials of structure, the value of x need be greater than 0.01, could guarantee the doped and substituted silicon position of Ti or Cr after; Can play the effect that improves the positive electrode performance; Preferably, 0.1≤x≤0.5, more preferably; 0.3≤x≤0.5 can make the specific capacity of positive electrode and high rate charge-discharge performance be highly improved.
The preferred M of the present invention is Mn
1-yFe
y, and 0.5≤y＜1; N is Ti, and promptly the structural formula of preferred positive electrode active materials is Li
2+xMn
1-yFe
ySi
1-xTi
xO
4, wherein, 0.3≤x≤0.5; 0.5 further optimize structure in≤y＜1, the solid solution structure of the positive electrode active materials of this kind structure better, more stable; The solid solubility that has manganese system and iron simultaneously and be two kinds of materials is better, and micro Distribution is more even, has not only further optimized the cycle performance of material; Simultaneously the shuttling back and forth and combine more conveniently of lithium ion further improved the conductivity of material.For example: the structural formula of the preferred positive electrode active materials of the present invention is Li
2Mn
0.5Fe
0.5Si
0.5Ti
0.5O
4The time, test XRD figure spectrum (consulting Fig. 1) can find out that material structure is single, no dephasign, and crystalline phase is purer, and capacity is high, excellent material performance.
Positive electrode of the present invention preferably also is coated with material with carbon element at the material surface of positive electrode active materials; Calculate by mass percentage; The content of said positive electrode active materials is 85wt%-95 wt %; The content of said material with carbon element is 5wt%-15 wt %, thereby further optimizes the electric conductivity and the surface topography of material.
The present invention provides the preparation method of above-mentioned positive electrode simultaneously, comprises the steps:
Step 1, with lithium source, M source, silicon source, N source mixing and ball milling, obtain mixed-powder;
Step 2, above-mentioned mixed-powder is heat-treated under inert atmosphere, obtaining structural formula is Li
2+xMSi
1-xN
xO
4Product, wherein, M is selected from Mn, Fe or Mn
1-yFe
y, N is selected from Ti, Cr or Ti
1-zCr
z, 0.01＜x≤0.5,0＜y＜1,0＜z＜1.
Above-mentioned preparation method's technology is simple, the excellent material performance for preparing simultaneously, Stability Analysis of Structures; Have the high rate charge-discharge performance, and the positive electrode for preparing is nano-particle material, the particle size distribution homogeneous of material; Particle diameter is distributed between the 50-100 nanometer, and crystalline form is perfect.
The mol ratio of Li:M:Si:N in preferred, lithium of the present invention source, M source, silicon source, the N source is (2-2.5): 1: (1-0.5): (0.01-0.5), can optimizing materials, optimize reaction.
The further preferred M of the present invention is manganese source and source of iron, and N is the titanium source, further optimizes the good Li of processability
2+xMn
1-yFe
ySi
1-xTi
xO
4, wherein, material property is further improved in 0.3≤x≤0.5,0.5≤y＜1.
Wherein, The present invention is to the not special restriction in lithium source, M source, N source, silicon source; Can be for well known to a person skilled in the art various lithiums source, M source, N source, silicon source, preferred, lithium for example of the present invention source is one or more in lithium carbonate, lithium oxalate, lithium acetate, lithium hydroxide, lithium chloride, lithium nitrate or the lithium fluoride.Said M source is selected from one or more in carbonate, oxalates, acetate, nitrate, chloride or the oxide of M; More preferably, said M source is selected from least a in manganese acetate, manganese carbonate, manganese nitrate, manganese oxalate, ferrous oxalate, frerrous chloride, the ferrous nitrate.Said silicon source is selected from one or more in nano silicon, aerosil, methyl silicate, tetraethoxysilane, Ludox, positive silicic acid or the silica gel.Said N source is selected from the chloride of N or in the oxide one or more, and more preferably, when N was Ti, the N source was a titanium dioxide, and when N was Cr, the N source was a chromium trioxide.
The medium of the preferred ball milling of the present invention is absolute ethyl alcohol or ethanol water, and wherein, water is 1:10-2:1 with the ratio of ethanol in the ethanol water, and the pH value of ethanol water is 7-12.More preferably, the medium of ball milling is an absolute ethyl alcohol, helps preparing the nano particle of uniform particle diameter, and particle should not be reunited.
Ball milling method of the present invention is for well known to a person skilled in the art various ball milling methods, for example: in raw material, add the zirconium ball of 800g ± 50 g, use planetary ball mill to be ball mill mixing under 300r/min ± 50r/min 5 hours ± 1 hour at rotating speed then.
The preferred heat treated temperature of the present invention is 650-850 ℃.The time of heating is preferably 8-20 hour.Heat treatment among the present invention is similar to sintering; And heat treatment can be that one section heat treatment also can be multistage heat treatment, preferred two sections heat treatments, and two sections heat treated processes are warming up to 350 ℃ ± 50 ℃ for the speed with 5 ℃/min ± 2 ℃/min; Under this temperature, be incubated 3 ± 1 hours; Speed with 8 ℃/min ± 2 ℃/min is warming up to 850 ℃ ± 50 ℃ then, under this temperature, is incubated 8h ± 2 hour, further optimizes the performance of material.
Inert atmosphere of the present invention is for well known to a person skilled in the art various inert atmospheres, and for example nitrogen, argon gas, hydrogen etc. are preferably the mist of mobile argon gas or argon gas and hydrogen, and flow velocity is 0.6L/min ± 0.1L/min.
The present invention further optimizes crystalline form and pattern, also comprises annealing in process after the preferred heat treatment, and wherein, the temperature of preferred annealing in process is 300-500 ℃; The time of annealing in process is 2-10 hour.For example can under 650 ℃, heat-treat 2 hours, after annealing was handled 6 hours down in 500 ℃, cooled to room temperature again with the furnace.
Also be added with the carbon source mixing and ball milling in the preferred steps 1 of the present invention, coat one deck carbon, increase conductivity on the surface of said positive electrode active materials.Wherein said carbon source is selected from one or more in sucrose, glucose, citric acid, ethylene glycol, the polyvinyl alcohol; Total weight with said positive electrode is a benchmark, and the addition of said positive electrode active materials is 85wt%-95 wt %, and the addition of said material with carbon element is 5wt%-15 wt %.
Below in conjunction with specific embodiment the present invention is done further detailed description.
Embodiment 1
(1) preparation of positive electrode
1), take by weighing 92.5g lithium carbonate, 30g aerosil, 57.5g manganese carbonate, 90g ferrous oxalate, 40g titanium dioxide and 5g sucrose, in the ethanol of 500ml, mix, use planetary ball mill to be ball milling 5h under the 300r/min then at rotating speed; 2) ball milling is good mixed-powder carries out the roasting heat processing in box atmosphere furnace; At flow velocity is under the Ar atmosphere protection of 0.6l/min, is warming up to 350 ℃ with the heating rate of 5 ℃/min, under this temperature, is incubated 10h; Heating rate with 8 ℃/min is warming up to 850 ℃ again; Under this temperature, be incubated 8h, cool to room temperature then with the furnace, obtain being coated with the Li of material with carbon element
2.5Mn
0.5Fe
0.5Si
0.5Ti
0.5O
4Active material;
Adopt Japan's public D/MAX2200PC model X-ray diffractometer of science (25 ℃ of room temperatures, radiation source are Cu target K alpha ray, tube voltage 40kV, tube current 20 mA, 10 °-80 ° of sweep limitss, step-length are the 0.01 °/s) Li of the above-mentioned preparation of test
2.5Mn
0.5Fe
0.5Si
0.5Ti
0.5O
4The XRD of active material (X ray crystal diffraction) figure, as shown in Figure 1, it is high by force to observe the active material peak, and crystalline form is perfect;
The JSM-6700F type field emission scanning electron microscope of company of employing NEC is observed the Li of above-mentioned preparation
2.5Mn
0.5Fe
0.5Si
0.5Ti
0.5O
4The FESEM of active material (field emission scanning electron microscope) figure, as shown in Figure 2, observe the Li that obtains above-mentioned preparation
2.5Mn
0.5Fe
0.5Si
0.5Ti
0.5O
4The particle size distribution of active material is 30-100nm, and average grain diameter is approximately 70 nanometers, and the grain diameter homogeneous is evenly distributed, no agglomeration;
(2) preparation of simulated battery:
Press mass ratio Li
2.5Mn
0.5Fe
0.5Si
0.5Ti
0.5O
4: nano carbon black: the mixed of PVDF=85:5:10, add organic solvent NMP (N-methyl pyrrolidone), be applied on the aluminium foil after fully stirring into even pastel, then in vacuum drying chamber in 110 ℃ of vacuumizes 8 hours; Cut-off directly is that the small pieces of 13mm are as positive pole; With the metal lithium sheet is negative pole; With the celgard2400 polypropylene porous film is barrier film; With 1.2mol/L LiPF
6(volume ratio is=4: as electrolyte, in being full of the Mbraun glove box of argon gas, assemble 1), obtain CR2016 type button cell A1 to be dissolved in the mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC).
Embodiment 2
Adopt to prepare positive electrode and simulated battery with embodiment 1 identical method, different is that the raw material that adds is lithium oxalate 112.1g, nano silicon 48g, manganese oxalate 28.6g, frerrous chloride 101.4g, chromium trioxide 20g and glucose 6g, preparation Li
2.2Mn
0.2Fe
0.8Si
0.8Cr
0.2O
4Active material, and make CR2016 type button cell A2.
Embodiment 3
Adopt to prepare active material and simulated battery with embodiment 1 identical method, different is that the raw material that adds is lithium nitrate 165.5g, Ludox 72.1g, manganese acetate 98.0g, ferrous nitrate 108g, titanium chloride 37.9g, chromium chloride 31.7g, citric acid 8g, preparation Li
2.4Mn
0.4Fe
0.6Si
0.6Ti
0.2Cr
0.2O
4Active material, and make CR2016 type button cell A3.
Embodiment 4
Adopt to prepare positive electrode and simulated battery with embodiment 1 identical method, different is that the raw material that adds is lithium nitrate 172.4g, Ludox 60.1g, ferrous nitrate 180g, titanium chloride 94.9g and citric acid 8g, preparation Li
2.5Fe
1.0Si
0.5Ti
0.5O
4Active material, and make CR2016 type button cell A5.
Comparative Examples 1
Adopt to prepare active material and simulated battery with embodiment 1 identical method, different is not add titanium source and chromium source in the raw material, prepares Li
2Mn
0.5Fe
0.5SiO
4Active material;
Adopting and recording the particle average grain diameter with embodiment 1 identical method is 300-1000nm, serious agglomeration, and particle is big, heterogeneity.
Performance test
1, specific capacity test: the battery of embodiment 1-4 and Comparative Examples 1 preparation placed carry out the charge-discharge performance test on the charge-discharge test appearance, the discharge voltage interval is 2-4.5V, and discharging current is 0.1C, and shown in Figure 3 is the Li of embodiment 1
2Mn
0.5Fe
0.5Si
0.5Ti
0.5O
4Discharge and recharge the first time of material and the curve chart that discharges and recharges for the second time, can find out that from curve chart the constant-current constant-voltage charging capacity can reach 317mAh/g first, discharge capacity is 243mAh/g; The constant-current constant-voltage charging capacity is 271mAh/g for the second time, and discharge capacity is 219mAh/g; Test result is listed in the table 1, and the test result of other embodiment 2-4 is seen table 1;
2, cycle performance test: the battery of embodiment 1-4 and Comparative Examples 1 preparation is placed Guangzhou Lan Qi Co., Ltd; Carry out the charge-discharge performance loop test on the charge-discharge test appearance of model BK-6016AR/2; The discharge voltage interval is 2-4.5V; Electric current is 0.1C, tests the residual capacity after the circulation 20 times, and test result is seen table 1;
3, high rate performance test: the battery of embodiment 1-4 and Comparative Examples 1 preparation is placed Guangzhou Lan Qi Co., Ltd; Carry out the constant current charge-discharge performance test on the charge-discharge test appearance of model BK-6016AR/2; The discharge voltage interval is 2-4.5V; Electric current is respectively 0.1C, 0.2C, 0.5C and 1C, and test result is seen table 2.
Table 1
Table 2
| ? | 0.1C the time specific discharge capacity mAh/g | 0.2C the time specific discharge capacity mAh/g | 0.5C the time specific discharge capacity mAh/g | Specific discharge capacity mAh/g during 1C |
| Embodiment 1 | 243 | 215.6 | 186.4 | 142.3 |
| Embodiment 2 | 230 | 190.3 | 145 | 128.6 |
| Embodiment 3 | 234 | 203.4 | 164.7 | 136.2 |
| Embodiment 4 | 232 | 198.2 | 152 | 131.7 |
| Comparative Examples 1 | 158.4 | 132.4 | 102.7 | 88.5 |
1-2 can know by table, and the positive electrode of embodiment of the invention 1-4 preparation has higher specific capacity, enclosed pasture efficient and better cycle performance compared to the positive electrode of Comparative Examples 1 preparation, and has excellent high rate charge-discharge performance.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the positive electrode of a lithium ion battery is characterized in that, said positive electrode comprises positive electrode active materials, and the structural formula of said positive electrode active materials is Li
2+xMSi
1-xN
xO
4, wherein, M is selected from Mn, Fe or Mn
1-yFe
y, N is selected from Ti, Cr or Ti
1-zCr
z, 0.01＜x≤0.5,0＜y＜1,0＜z＜1.
2. positive electrode according to claim 1 is characterized in that, said M is Mn
1-yFe
y, N is Ti, 0.1≤x≤0.5,0.5≤y＜1.
3. positive electrode according to claim 1; It is characterized in that the surface of said positive electrode active materials also is coated with material with carbon element, in said positive electrode; The content of said positive electrode active materials is 85wt%-95 wt %, and the content of said material with carbon element is 5wt%-15 wt %.
4. the preparation method of the positive electrode of a lithium ion battery is characterized in that, comprises the steps:
Step 1, with lithium source, M source, silicon source, N source mixing and ball milling, obtain mixed-powder;
Step 2, above-mentioned mixed-powder is heat-treated under inert atmosphere, obtaining structural formula is Li
2+xMSi
1-xN
xO
4Product, wherein, M is selected from Mn, Fe or Mn
1-yFe
y, N is selected from Ti, Cr or Ti
1-zCr
z, 0.01＜x≤0.5,0＜y＜1,0＜z＜1.
5. preparation method according to claim 4 is characterized in that, the mol ratio of the Li:M:Si:N in said lithium source, M source, silicon source, the N source is (2-2.5): 1: (1-0.5): (0.01-0.5).
6. preparation method according to claim 4 is characterized in that, said lithium source is selected from one or more in lithium carbonate, lithium oxalate, lithium acetate, lithium hydroxide, lithium chloride, lithium nitrate or the lithium fluoride;
Said M source is selected from one or more in carbonate, oxalates, acetate, nitrate, chloride or the oxide of M;
Said N source is selected from the chloride of N or in the oxide one or more;
Said silicon source is selected from one or more in nano silicon, aerosil, methyl silicate, tetraethoxysilane, Ludox, positive silicic acid or the silica gel.
7. preparation method according to claim 6; It is characterized in that; Said M source is selected from least a in manganese acetate, manganese carbonate, manganese nitrate, manganese oxalate, ferrous oxalate, frerrous chloride, the ferrous nitrate, and said N source is selected from least a in titanium dioxide, the chromium trioxide.
8. preparation method according to claim 4 is characterized in that, the medium of said ball milling is an absolute ethyl alcohol.
9. preparation method according to claim 4 is characterized in that, in step 1, also is added with the carbon source mixing and ball milling, and said carbon source is selected from one or more in sucrose, glucose, citric acid, ethylene glycol, the polyvinyl alcohol.
10. the preparation method of positive electrode active materials according to claim 4 is characterized in that, said inert atmosphere is the mist of argon gas or argon gas and hydrogen; Said heat treated temperature is 650-850 ℃, and the time is 8-20 hour.
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| CN106602046A (en) * | 2017-02-23 | 2017-04-26 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery silicate cathode material, and preparation and application thereof |
| CN106784625A (en) * | 2017-02-10 | 2017-05-31 | 济南大学 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN112467122A (en) * | 2020-12-03 | 2021-03-09 | 松山湖材料实验室 | Lithium orthosilicate composite material and preparation method and application thereof |
| CN113948698A (en) * | 2021-10-14 | 2022-01-18 | 浙江长兴中俄新能源材料技术研究院有限公司 | Preparation method of nano polyanionic material carbon composite lithium iron silicate |
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| CN1458705A (en) * | 2002-05-13 | 2003-11-26 | 三星Sdi株式会社 | Method for preparing positive active matter of lithium secondary battery |
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| CN106784625A (en) * | 2017-02-10 | 2017-05-31 | 济南大学 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN106602046A (en) * | 2017-02-23 | 2017-04-26 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery silicate cathode material, and preparation and application thereof |
| CN106602046B (en) * | 2017-02-23 | 2020-01-17 | 中国科学院宁波材料技术与工程研究所 | Silicate positive electrode material of lithium ion battery and preparation and application thereof |
| CN112467122A (en) * | 2020-12-03 | 2021-03-09 | 松山湖材料实验室 | Lithium orthosilicate composite material and preparation method and application thereof |
| CN113948698A (en) * | 2021-10-14 | 2022-01-18 | 浙江长兴中俄新能源材料技术研究院有限公司 | Preparation method of nano polyanionic material carbon composite lithium iron silicate |
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