CN102244236A - Method for preparing lithium-enriched cathodic material of lithium ion battery - Google Patents
Method for preparing lithium-enriched cathodic material of lithium ion battery Download PDFInfo
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- CN102244236A CN102244236A CN2011101551510A CN201110155151A CN102244236A CN 102244236 A CN102244236 A CN 102244236A CN 2011101551510 A CN2011101551510 A CN 2011101551510A CN 201110155151 A CN201110155151 A CN 201110155151A CN 102244236 A CN102244236 A CN 102244236A
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- lithium
- rich
- oxalate
- manganese
- salt
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 60
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000010406 cathode material Substances 0.000 title claims abstract 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 22
- 239000011572 manganese Substances 0.000 claims abstract description 60
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 18
- 229940039748 oxalate Drugs 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 6
- 229940039790 sodium oxalate Drugs 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 5
- 229930003268 Vitamin C Natural products 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 235000019154 vitamin C Nutrition 0.000 claims description 5
- 239000011718 vitamin C Substances 0.000 claims description 5
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 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
- 238000002156 mixing Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims 1
- 229940044175 cobalt sulfate Drugs 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- -1 oxalate ions Chemical class 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 238000009827 uniform distribution Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 42
- 238000000975 co-precipitation Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 229910052748 manganese Inorganic materials 0.000 abstract description 8
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000006104 solid solution Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 description 31
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 12
- 229910001947 lithium oxide Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910015645 LiMn Inorganic materials 0.000 description 4
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 150000003891 oxalate salts Chemical class 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000002641 lithium Chemical class 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910003003 Li-S Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003834 hydroxide co-precipitation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- GANDVAJEIJXBQJ-UHFFFAOYSA-M potassium;hydron;2-hydroxy-2-oxoacetate Chemical compound [K+].OC(=O)C(O)=O.OC(=O)C([O-])=O GANDVAJEIJXBQJ-UHFFFAOYSA-M 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 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
本发明提出了一种制备富锂正极材料Li[LixMnyM(1-x-y)]O2(0＜x，y＜0.5，M＝Mn0.5Ni0.5或M＝Mnx’Niy’Co(1-x’-y’)，0＜x’，y’＜0.5)的方法。首先，利用水热辅助草酸盐共沉淀法制备稳定的前驱体，这样可以避免二价锰(II)在溶液中被空气氧化，最后得到Ni、Co和Mn等金属元素达到原子级均匀分布的草酸盐固溶体，并使得制备的富锂正极材料具有很高的电化学活性；其次，利用原位还原氧化石墨烯的方法，在富锂材料表面均匀包覆一层具有高电导率的石墨烯材料，可以明显改善富锂材料的倍率性能和循环稳定性能。该制备方法在反应过程不用惰性气体保护，简化了反应，节省了成本；所制备的富锂正极材料颗粒均匀，电化学活性高，比容量大于250mAh/g；产物倍率性能和循环稳定性能良好；该制备方法工艺重复性好，不同批次制备的材料物化性能波动很小。
The present invention proposes a preparation of lithium-rich cathode material Li[Li x Mn y M (1-xy) ]O 2 (0<x, y<0.5, M=Mn 0.5 Ni 0.5 or M=Mn x' Ni y' Co (1-x'-y') , 0<x', y'<0.5) method. Firstly, a stable precursor was prepared by hydrothermal assisted oxalate co-precipitation method, which can avoid the oxidation of divalent manganese(II) by air in the solution, and finally obtain metal elements such as Ni, Co and Mn that are evenly distributed at the atomic level. oxalate solid solution, and make the prepared lithium-rich cathode material have high electrochemical activity; secondly, use the method of in-situ reduction of graphene oxide to uniformly coat a layer of graphene with high conductivity on the surface of the lithium-rich material materials, which can significantly improve the rate performance and cycle stability of lithium-rich materials. The preparation method does not require inert gas protection during the reaction process, which simplifies the reaction and saves costs; the prepared lithium-rich cathode material has uniform particles, high electrochemical activity, and a specific capacity greater than 250mAh/g; the product rate performance and cycle stability are good; The preparation method has good process repeatability, and the fluctuation of physical and chemical properties of materials prepared in different batches is small.
Description
Technical field:
The invention belongs to chemical power source material preparation and anode material for lithium-ion batteries field, relate to a kind of method for preparing anode material for lithium-ion batteries.
Background technology
Advantages such as it is big that lithium ion battery has energy density, has extended cycle life, in light weight, pollution-free are the efficient portable chemical power supplys of a new generation.Aspects such as radio communication, digital camera, notebook computer and space technology have been widely used in now.Along with the further lifting of lithium ion battery energy density and power density, will progressively be applied to fields such as electric tool, electric bicycle, electric automobile (EV), hybrid vehicle (HEV) and extensive accumulate.
Positive electrode plays decisive role to the battery performance of lithium-ion-power cell, fail safe, cost etc., and its development has been subjected to extensive concern, and has urgency.
Present stage, main commercial anode material for lithium-ion batteries was mainly LiCoO
2, LiFePO
4, LiMn
2O
4, LiMn
xNi
yCo
(1-x-y)O
2(0＜x, y＜0.5) etc.LiCoO wherein
2Because Co
3+Have toxicity, and cobalt is scarce resource, material cost height, poor stability; LiMn
2O
4Capacity has only about 120mAh/g, and capacity is on the low side, and in cyclic process the Jahn-Teller distortion takes place easily, influences the stable circulation performance of material, and the high-temperature behavior of material is also not good enough; LiFePO
4Because its intrinsic electronics and ionic conductivity are poor, and be difficult to synthetic pure phase, and realization capacity and tap density are taken into account.The nearly stage, new system lithium ion battery Li-S battery is subjected to people and pays close attention to, wherein the reversible capacity of positive electrode S reaches more than the 800mAh/g, but be faced with the decay that the shuttle phenomenon causes its capacity that flies that its polysulfide dissolves in electrolyte, the cyclical stability of material is relatively poor, and the simple substance lithium forms the SEI film easily on the surface, dendrite, the problems such as deposition of polysulfide of dissolving influence the cyclicity, particularly fail safe of material.LiMn
xNi
yCo
(1-x-y)O
2(0＜x, y＜0.5) comprehensive LiCoO
2, LiMnO
2And LiNiO
2Advantage, obtain the concern of a lot of research groups.And the another kind that is all this type of stratified material is based on rock salt structure Li
2MnO
3Lithium-rich anode material Li[Li
xMn
yM
(1-x-y)] O
2(0＜x, y＜0.5, M=Mn
0.5Ni
0.5Or M=Mn
X 'Ni
Y ' Co
(1-x '-y ')0＜x ', y '＜0.5) begins in recent years extensively to be paid close attention to, the specific capacity of this type of material is up to 200mAh/g～300mAh/g (about theoretical capacity 300mAh/g), can satisfy the demand of following lithium-ion-power cell high-energy-density, also be hopeful most present stage, one of the most potential power lithium-ion battery positive electrode.
Canada Jeff Dahn research group is precipitation reagent with LiOH, synthetic precursor Ni
xMn
(1-x)(OH)
2, prepare the binary lithium-rich anode material Li[Ni of excellent performance first
xLi
1/3-2x/3Mn
2/3-x/3] O
2Korea S Hong and Park research group adopt the synthetic rich lithium material Li[Ni of simple combustion method with the colloidal sol precursor
xLi
1/3-2x/3Mn
2/3-x/3] O
2, discharge capacity reaches as high as 288mAh/g first when 20mA/g.Japan NEDO subsidizes a class Li of research and development
1+x(Fe
0.2Ni
0.2Mn
0.6)
1-xO
2Rich its specific discharge capacity of lithium material also can be greater than 250mAh/g.The Yang Han of Wuhan University west group adopts the synthetic preferable Li[Li of performance of polymer method for pyrolysis
0.12Ni
0.32Mn
0.56] O
2The Chen Gang of Jilin University, Wei Ying enter group lithium ion kinetics of diffusion in the rich lithium are studied.
Patent application " lithium-rich manganese-based anode material and preparation method thereof " (application number: 200910186311.0) disclose lithium-rich manganese-based anode material Li[Li
(1-2x)/3Ni
X-aM
yMn
(2-x)/3-b] O
2(M=Co, Al, Ti, Mg, Cu) and preparation method thereof; Patent application " a kind of method of modifying of high-rate lithium-rich material " (application number: 200910085461.2) disclose a kind of to lithium-rich anode material Li[Li
xNi
1/3-2x/Mn
2/3-x/3] O
2MnO carries out (1/5≤x≤1/3)
2Coat the method for improving the material high rate performance of handling; A kind of cobalt nickel oxide manganses lithium anode material of rich lithium type layer structure has been announced in patent application " lithium ion battery positive pole material cobalt nickel oxide manganses lithium " (application number 200610130302.6); Patent application " a kind of preparation method of composite anode material of high-capacity lithium ion battery " (application number: 200910303612.7,200910043712.0) disclose the method for utilizing ball milling to prepare lithium-rich anode material in conjunction with solid-phase sintering process; Patent application " a kind of anode material for lithium-ion batteries Li
1+x(Co
yMn
zNi
1-y-z)
1-xO
2And preparation method thereof " (application number: 200610150194.9) disclose a kind of soluble inorganic salt solution and solubility strong base solution prepared by co-precipitation presoma of utilizing, generated the method for lithium-rich anode material again with the lithium-containing compound sintering.
In the preparation technology of this class lithium-rich anode material, whether Ni, Co and Mn distribution evenly is the key factor that influences material structure and chemical property in the presoma.Current the most frequently used preparation method is a hydroxide coprecipitation step, promptly prepares Ni, Co, Mn hydroxide co-precipitation presoma earlier, and then adds lithium salts, makes after high-temperature process.This is that the dispersion of Ni, Co and Mn is very even because of in Ni, Co, the Mn precipitation of hydroxide, and the rich lithium material that makes at last has better crystalline form, and performance is also good than additive methods such as high temperature solid-state methods.Yet bivalent manganese in the hydroxide coprecipitation step preparation process (II) easily is oxidized to tetravalence manganese (IV), causes preparation technology's poor repeatability, easily produces dephasign, and the product fluctuation is big, thereby has had a strong impact on the performance of end product.Therefore, when hydroxide coprecipitation step prepares material, usually need to use argon shield, this makes that reaction is complicated, has increased the control difficulty, and the use of argon gas has simultaneously improved cost.
Given this, we do oxalate precipitation reagent first and are incorporated in rich lithium material synthetic, as the synthetic rich lithium material of precursor, make the embedding of material take off the reason capacity and cycle performance obviously improves with oxalic acid unit coprecipitate stable under the non-alkali condition of normal temperature.
In addition, though rich lithium material Li[Li
xMn
yM
(1-x-y)] O
2(0＜x, y＜0.5, M=Mn
0.5Ni
0.5Or M=Mn
X 'Ni
Y 'Co
(1-x '-y '), 0＜x ', y '＜0.5) and have high specific capacity, but studies show that both at home and abroad there is following problem in this class material: the electron conduction of material intrinsic and ionic conductivity be not good to cause high rate performance, heavy-current discharge performance poor; For the stability of material property, there is very big-difference in the report of different documents; The erosion that composition in the material is subjected to electrolyte causes cyclicity not good; The first charge-discharge efficiency of material is lower.
Therefore, at the problem of rich lithium material in high rate performance and stable circulation performance, the present invention utilizes graphene oxide to be reduced into the method for Graphene at rich lithium material surface in situ, plan is improved the multiplying power and the cycle performance of material by the Graphene that even coating-doping has high conductivity and high structural stability.For solving the crucial difficult point that this class material is applied to power battery anode material, should set about from preparation technology's innovation, solution is proposed.
Summary of the invention:
Purpose of the present invention is exactly at lithium-rich anode material Li[Li
xMn
yM
(1-x-y)] O
2(0＜x, y＜0.5, M=Mn
0.5Ni
0.5Or M=Mn
X 'Ni
Y 'Co
(1-x '-y '), 0＜x ', y '＜0.5) and the problem that exists, a kind of new preparation method has been proposed, this method is with low cost, and is simple and easy to do.At first, the presoma of oxalate coprecipitation method preparation is more stable, can avoid bivalent manganese (II) oxidation by air in solution, obtain metallic elements such as Ni, Co and Mn at last and reach the equally distributed oxalates solid solution of atom level, make the lithium-rich anode material of preparation have very high electro-chemical activity.Secondly, utilize the method for in-situ reducing graphene oxide,, can obviously improve the high rate performance and the stable circulation performance of rich lithium material at the grapheme material that rich lithium material coated with uniform one deck has high conductivity.
The present invention is achieved through the following technical solutions:
Nickel salt, cobalt salt and manganese salt are dissolved in the deionized water with certain stoichiometric proportion, stir, obtain even mixed solution; Press the total mole number of metal ion in nickel salt, cobalt salt and the manganese salt, take by weighing the oxalic acid that contains identical molal quantity oxalate denominationby or the oxalates of solubility, be dissolved in and obtain second kind of aqueous solution in the deionized water; Above-mentioned two kinds of aqueous solution equal-volumes are splashed in the reactor of continuous stirring uniformly, after fully mixing reactor is sealed, place 100～200 ℃ of baking ovens, continue reaction 3～24 hours, cooling, obtain the oxalate coprecipitation thing that nickel cobalt manganese is evenly distributed, in precipitation process, the pH value of solution is controlled between 4～8.5; Coprecipitate after filtration, washing, dry back obtain precursor with even mixing of the lithium salts of certain stoichiometric proportion, in air atmosphere that precursor is first 400～600 ℃ of following constant temperature pre-burnings 3～8 hours, be pressed into sheet then, obtained rich lithium oxide Li[Li in 6～18 hours at 700 ℃～950 ℃ sintering temperatures again
xMn
yM
(1-x-y)] O
2(0＜x, y＜0.5, M=Mn
0.5Ni
0.5Or M=Mn
X 'Ni
Y 'Co
(1-x '-y '), 0＜x ', y '≤0.5); Rich lithium oxide is ground to form the powder of particle diameter at 0.1～1 μ m, the utilization sonicated, powder is dispersed in the single or multiple lift graphite oxide aqueous solution that concentration is 0.1～10mg/ml, the vitamin C aqueous solution that adds certain stoichiometric proportion then, stir, make graphene oxide be reduced into Graphene, after filtration, washing and dry, obtain the lithium ion battery lithium-rich anode material at rich lithium oxide powder surface in situ.
The oxalates of above-mentioned solubility is one or several in sodium oxalate, potassium oxalate, potassium tetroxalate dihydrate and the ammonium oxalate.
Above-mentioned nickel salt is one or more in nickel acetate, nickel nitrate, nickelous sulfate and the nickel chloride; Above-mentioned cobalt salt is one or more in cobalt acetate, cobalt nitrate, cobaltous sulfate and the cobalt chloride, and above-mentioned manganese salt is one or more in manganese acetate, manganese nitrate, manganese sulfate and the manganese chloride.
Above-mentioned lithium-containing compound is one or several in lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate and the lithium chloride.
Above-mentioned graphite oxide aqueous solution makes by the acid system stripping technology, and with low cost, purity is higher.
The invention has the advantages that:
First, owing to replace hydroxide as precipitation reagent with oxalates, reaction generates oxalate precipitation, because manganese oxalate (II) is more stable in water than manganous hydroxide (II), therefore avoided the oxidation of bivalent manganese (II), thereby avoided the generation of dephasign, not blanketing with inert gas of course of reaction when using coprecipitation to prepare precursor, simplified reaction, provided cost savings; Product electro-chemical activity height, specific capacity be greater than 250mAh/g, good cycle; And this method good process repeatability, the fluctuation of product physical and chemical performance is little.
The second, adopt graphene oxide in-situ reducing technology, can realize the even coating of Graphene to rich lithium material, can obviously improve the multiplying power and the stable circulation performance of rich lithium material.
Description of drawings
Fig. 1 adopts the lithium-rich anode material Li[Ni of the inventive method preparation
0.2Li
0.2Mn
0.6] O
2The XRD diffracting spectrum.
Fig. 2 adopts the lithium-rich anode material Li[Ni of the inventive method preparation
0.2Li
0.2Mn
0.6] O
2Stereoscan photograph.
Fig. 3 adopts the lithium-rich anode material Li[Ni of the inventive method preparation
0.2Li
0.2Mn
0.6] O
2The cycle performance curve.
Embodiment
Embodiment 1: preparation lithium-rich anode material Li[Ni
0.2Li
0.2Mn
0.6] O
2, i.e. Li[Li
xMn
yM
(1-x-y)] O
2(x=0.2, y=0.2, M=Mn
0.5Ni
0.5).
At room temperature, mixture of a certain amount of nickel nitrate, manganese nitrate (wherein the ratio of nickel ion and manganese ion is 1: 1) and ammonium oxalate are dissolved in the water respectively.Ammonium oxalate solution and mixture solution are evenly splashed in the reactor, fully mix, reaction with the reactor sealing, places 180 ℃ of baking ovens then, and 12 as a child took out, and natural cooling generates the oxalate coprecipitation that nickel manganese is evenly distributed.With oxalate precipitation for several times, filter oven dry with deionized water wash.A certain amount of lithium carbonate of the precipitation powder of oven dry is ground evenly,, be pressed into sheet after the cooling, calcine down at 850 ℃ and obtained well-crystallized, the rich lithium oxide Li[Ni that chemical property is good in 12 hours 450 ℃ of following constant temperature pre-burnings 6 hours
0.2Li
0.2Mn
0.6] O
2With rich lithium oxide grind into powder, the utilization sonicated, powder is dispersed in the single or multiple lift graphite oxide aqueous solution that concentration is 3mg/ml, the vitamin C aqueous solution that adds certain stoichiometric proportion then, stir, make graphene oxide be reduced into Graphene, after filtration, washing and dry, obtain the lithium ion battery lithium-rich anode material at rich lithium oxide powder surface in situ.
Figure of description Fig. 1 is this lithium-rich anode material Li[Ni just
0.2Li
0.2Mn
0.6] O
2The XRD figure spectrum of sample.Can observe some more weak diffraction maximums in the XRD figure spectrum between 2 θ=20 °～25 °, these diffraction maximums are because Li
+And Mn
4+Cause at the transition metal layer orderly arrangement in more among a small circle formation superlattice.Li in the C2/m space group
2MnO
3Structure cell in, Li
+And Mn
4+In transition metal layer, arrange in order, therefore in its standard x RD spectrogram, also have 20 °～25 ° characteristic diffraction peak.And at Li[Ni
0.2Li
0.2Mn
0.6] O
2XRD spectra in faint diffraction maximum between having occurred 20 °～25 °, show at internal memory more among a small circle at small Li
2MnO
3The phase farmland shows Li[Ni
0.2Li
0.2Mn
0.6] O
2Be with Li
2MnO
3-LiNi
0.5Mn
0.5O
2The form of solid solution exists.Except these the faint diffraction maximums between 20 °～25 °, other stronger diffraction peak intensities are all very high, these diffraction maximums and LiNi
0.5Mn
0.5O
2Characteristic diffraction peak is similar, can simply that these are stronger diffraction maximum belongs to have the symmetric O of R-3m
3-LiCoO
2The characteristic peak of the layer structure of type.The XRD figure spectrum goes up (006)/(102) in addition and the two pairs of clear ground cleaves in peak in (008)/(110) separately come, and shows synthetic Li[Ni
0.2Li
0.2Mn
0.6] O
2Show good layer structure feature.
Figure of description Fig. 2 is this lithium-rich anode material Li[Ni
0.2Li
0.2Mn
0.6] O
2The sem photograph of sample, material granule is spherical as can be seen from Figure 2, and the average diameter of particle is less than 500nm, and having among a small circle reunites takes place, and the floccule of particle surface is a grapheme material.
Figure of description Fig. 3 is this lithium-rich anode material Li[Ni
0.2Li
0.2Mn
0.6] O
2The discharge capacity cycle graph of sample.First discharge specific capacity is at 228mAh/g, and discharge capacity rises to 260mAh/g after the circulation of 10 weeks, is being recycled to for the 30th week, and reversible specific discharge capacity still remains on about 260mAh/g.
Embodiment 2: preparation lithium-rich anode material Li[Li
0.2Mn
0.54Co
0.13Ni
0.13] O
2, i.e. Li[Li
xMn
yM
(1-x-y)] O
2(x=0.2, y=0.4, M=Mn
0.5Ni
0.5Co
0.5).
At room temperature, mixture of a certain amount of nickelous sulfate, cobaltous sulfate and manganese sulfate (wherein the ratio of nickel ion, cobalt ions and manganese ion is 1: 1: 1) and sodium oxalate are dissolved in the water respectively.Sodium oxalate solution and mixture solution are evenly splashed in the reactor, fully mix, reaction with the reactor sealing, places 200 ℃ of baking ovens then, and 12 as a child took out, and natural cooling generates the oxalate coprecipitation that nickel cobalt manganese is evenly distributed.With oxalate precipitation for several times, filter oven dry with deionized water wash.A certain amount of lithium carbonate of the precipitation powder of oven dry is ground evenly,, be pressed into sheet after the cooling, calcine down at 800 ℃ and obtained well-crystallized, the rich lithium oxide Li[Li that chemical property is good in 15 hours 500 ℃ of following constant temperature pre-burnings 5 hours
0.2Mn
0.54Co
0.13Ni
0.13] O
2With rich lithium oxide grind into powder, the utilization sonicated, powder is dispersed in the single or multiple lift graphite oxide aqueous solution that concentration is 5mg/ml, the vitamin C aqueous solution that adds certain stoichiometric proportion then, stir, make graphene oxide be reduced into Graphene, after filtration, washing and dry, obtain the lithium ion battery lithium-rich anode material at rich lithium oxide powder surface in situ.
XRD test shows Li[Li
0.2Mn
0.54Co
0.13Ni
0.13] O
2Be with Li
2MnO
3-LiNi
0.5Mn
0.5O
2The form of solid solution exists.The surface sweeping electron microscopic observation finds that the average diameter of particle is less than 400nm.The constant current charge-discharge experiment shows that the reversible doff lithium capacity of material reaches 289mAh/g.
Embodiment 3: preparation lithium-rich anode material Li[Li
0.2Mn
0.4Co
0.2Ni
0.2] O
2, i.e. Li[Li
xMn
yM
(1-x-y)] O
2(x=0.2, y=0.2, M=Mn
0.5Ni
0.5Co
0.5).
At room temperature, mixture of a certain amount of nickelous sulfate, cobaltous sulfate and manganese sulfate (wherein the ratio of nickel ion, cobalt ions and manganese ion is 1: 1: 1) and sodium oxalate are dissolved in the water respectively.Sodium oxalate solution and mixture solution are evenly splashed in the reactor, fully mix, reaction with the reactor sealing, places 150 ℃ of baking ovens then, and 18 as a child took out, and natural cooling generates the oxalate coprecipitation that nickel cobalt manganese is evenly distributed.With oxalate precipitation for several times, filter oven dry with deionized water wash.A certain amount of lithium carbonate of the precipitation powder of oven dry is ground evenly,, be pressed into sheet after the cooling, calcine down at 900 ℃ and obtained well-crystallized, the rich lithium oxide Li[Li that chemical property is good in 10 hours 550 ℃ of following constant temperature pre-burnings 4.5 hours
0.2Mn
0.4Co
0.2Ni
0.2] O
2With rich lithium oxide grind into powder, the utilization sonicated, powder is dispersed in the multilayer graphite oxide aqueous solution that concentration is 4mg/ml, the vitamin C aqueous solution that adds certain stoichiometric proportion then, stir, make graphene oxide be reduced into Graphene, after filtration, washing and dry, obtain the lithium ion battery lithium-rich anode material at rich lithium oxide powder surface in situ.
XRD test shows Li[Li
0.2Mn
0.4Co
0.2Ni
0.2] O
2Be with Li
2MnO
3-LiNi
0.5Mn
0.5O
2The form of solid solution exists.The surface sweeping electron microscopic observation finds that the average diameter of particle is less than 500nm.The constant current charge-discharge experiment shows that the reversible doff lithium capacity of material is greater than 280mAh/g.
Claims (4)
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