CN1450676A - Lithium ion positive electrode material and preparation method thereof - Google Patents
Lithium ion positive electrode material and preparation method thereof Download PDFInfo
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- CN1450676A CN1450676A CN03114397A CN03114397A CN1450676A CN 1450676 A CN1450676 A CN 1450676A CN 03114397 A CN03114397 A CN 03114397A CN 03114397 A CN03114397 A CN 03114397A CN 1450676 A CN1450676 A CN 1450676A
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- lithium ion
- anode material
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- ion anode
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Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 47
- 239000007774 positive electrode material Substances 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 16
- 239000011029 spinel Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000006259 organic additive Substances 0.000 claims abstract description 5
- 239000010405 anode material Substances 0.000 claims description 42
- 238000005868 electrolysis reaction Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- -1 alkali metal salt Chemical class 0.000 claims description 19
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910052759 nickel 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
- 238000005245 sintering Methods 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 150000001413 amino acids Chemical class 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 150000002484 inorganic compounds Chemical group 0.000 claims description 5
- 229910010272 inorganic material Inorganic materials 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000005840 aryl radicals Chemical group 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 2
- 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 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004075 acetic anhydrides Chemical class 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 159000000032 aromatic acids Chemical class 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 4
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 abstract 1
- 150000001447 alkali salts Chemical class 0.000 abstract 1
- 239000002585 base Substances 0.000 abstract 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 abstract 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 229910012820 LiCoO Inorganic materials 0.000 description 13
- 239000011572 manganese Substances 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- KFKJUYCIGRHJCF-UHFFFAOYSA-N cobalt;ethanol Chemical compound [Co].CCO KFKJUYCIGRHJCF-UHFFFAOYSA-N 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 239000000376 reactant Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 description 6
- 150000004692 metal hydroxides Chemical class 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000009856 non-ferrous metallurgy Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910018871 CoO 2 Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910018680 LixCo Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- ZFSQRSOTOXERMJ-UHFFFAOYSA-N ethanol;iron Chemical compound [Fe].CCO.CCO.CCO ZFSQRSOTOXERMJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000299 transition metal carbonate Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- UYDMXQQVXGMPKK-UHFFFAOYSA-N vanadium;trihydrate Chemical compound O.O.O.[V] UYDMXQQVXGMPKK-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
This invention discloses a Li ion positive material and its preparation method solving the problem of reducing the circulation attenuation of the positive ionic material with the oxide general formula: xA2O.yM2Om.zN2On, the material is composed of 2-D hexagonal laminated crystal, compound oxide crystal of 3-D spinel structure or lithium vanadium oxide in the following processing steps: to electrolyse metal directly to form metal alkoxide in alcohol soluble absolute electrolyte containing organic additives then to mix with solution with assistant alkali salt or base to form positive sol precursor to dry to remove the solvent and form positive powder precursor under 120 to 550 deg.C. to process in solid phase reaction for 0.5-48h in 450-960 deg.c.
Description
Technical field
The present invention relates to a kind of anode material for lithium ion battery and preparation method thereof, particularly a kind of anode active material of lithium ion battery and electrochemical method for synthesizing thereof.
Background of invention
As the anodal active insert material of lithium ion battery, the focus of research and development mainly concentrates on Li
xCoO
2, Li
xNiO
2, Li
xMn
2O
4, Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13, with and the derivative of modification or doping, promptly partly substitute Co, Ni, Mn and V in the above composite oxides, the LixCo of formation with other metallic element
1-αM
αO
2, Li
xNi
1-αM
αO
2, wherein: 0＜x＜1.1,0≤α≤1, M=Co, Ni, Mn, V, Al or Cr etc.,, Li
xMn
2-αM
αO
4, wherein: 0＜x＜1.1,0≤α≤2, M=Co, Ni, V, Al or Cr etc.Li
xCoO
2On combination properties such as specific capacity, fail safe and loop attenuation is best material at present, has realized large-scale production and commercial applications.Li
xMn
2O
4The system material charge discharge is safe, but specific capacity is low, and loop attenuation is fast; Li
xNiO
2And Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13Specific capacity be higher than Li
xCoO
2, fatal shortcoming is that loop attenuation is fast, discharges and recharges poor stability.
The method of synthesizing lithium ion battery material is concluded three classes is roughly arranged at present, promptly direct high temperature solid phase synthesis, indirect solid-phase synthesis and outer field action synthetic method.Directly high temperature is synthetic comprises that traditional solid-state chemical reaction is synthetic, fused salt is synthetic and ion-exchange, and solid-state reactants is carried out high temperature, about 900 ℃ of reactions after mixing.Between be bonded into and comprise so-gel, precipitation from homogeneous solution and co-precipitation, spray drying, spray pyrolysis, freeze drying, and emulsification dispersion method, hydro-thermal is synthetic, and hydrothermal oxidization is synthetic, and these methods belong to the pre-treatment means of solid phase reaction, purpose is for improving the mixing uniformity of reactant, the predecessor that the preparation metal ion is evenly distributed.Also there are some problems that need solve in these technologies of preparing.
Directly the synthetic method material is by mechanical crushing and physical mixed, and the process of solid state reaction is by the infiltration diffusion control on solid phase particles surface, and reaction time is long.The main difficult point of indirect synthetic method, the physics and the chemical property difference that are transition metal such as Cobalt, nickel, vanadium and manganese compound and alkali metal lithium compound are big, solubility product as transition metal hydroxide is very low, and alkali-metal hydroxide has higher solubility in water; In addition, the solubility product constant Ksp of transition metal and alkali-metal carbonate differs greatly, except that the carbonate of nickel and lithium differs 5 orders of magnitude, other differs about 10 orders of magnitude mostly, so utilize these indirect solid reaction processes, it is very difficult to prepare the homodisperse pre-reaction material of each metal ion species cost-effectively, takes place easily in the solid phase reaction process to form segregation phenomena, generally contains dephasign in the product.
The synthetic method of synthesizing lithium ion battery anode powder under the outer field action has two kinds of microwave method and electric field electrolysis metal methods.The former used material is identical with direct high temperature solid phase synthesis, and problem is that reaction is incomplete, and the crystal structure of material is imperfect, and chemical property is poor.Chinese invention patent application number 02123800.6, open day on December 25th, 2002, the preparation method of title lithium ion secondary battery anode material, be direct electrolytic metal Cobalt, metallic nickel or Cobalt nickel alloy, electrolysate is converted into the oxide of Cobalt or nickel, is mixed with lithium ion secondary battery anode material with lithium salts again.Chinese invention patent application number 95190471.X, in open day on June 4th, 1997, name is called the electrochemical method and the equipment of preparation metal hydroxides and/or metal oxide hydroxide, Chinese invention patent application number 92113469.X, in open day on June 2nd, 1993, name is called the electricity consumption solution and prepares metal oxide sol, and these two patent applications are the electrolytic preparation metal oxide, the former is with Co, Ni, Cu, Fe, In, Mn, Sn, Zn, Ti, Al, Cd, U are anode, in the presence of the complexing of metal ion agent, the oxyhydroxide of synthetic corresponding metal hydroxide or metal.The latter is the aqueous solution of electrolytic metal salt, prepares the method for monobasic or multi-element metal oxide colloidal sol.
The electrolyzing synthesizing method of these several metal oxides or hydrous oxide, all be electrolyte with the aqueous solution, deposit following problem: one, because the solubility product constant of Cobalt (II), Cobalt (III), nickel (II), manganese (II), vanadium (III) hydroxide, represent, be respectively 14.2 with the negative logarithm-lgKsp of solubility product constant, 44.5,15.2,12.8,34.3, its hydroxide or metal oxide are easy to form passivation layer at electrode surface, and current efficiency is descended; Two, directly form the colloidal solid of corresponding metal hydroxide or metal oxide in the electrolysis unit, can reduce the conductance of electrolyte, need constantly to adjust the pH value and the conductivity of electrolyte, at stable condition, carry out under constant current and the polar plate voltage to guarantee electrolysis; Three, electrolytic process release heat, the temperature of electrolysis tank electrolyte inside generally 40 ℃～70 ℃ scopes, can be quickened the hydrolysis of transition metal ions.
Summary of the invention
The purpose of this invention is to provide a kind of anode material for lithium-ion batteries and preparation method thereof, the technical problem that solves is to reduce the loop attenuation of anode material for lithium-ion batteries, improve specific capacity, second technical problem that the present invention will solve is to improve electrode surface current efficiency in the electrolytic process, and electrolysis is carried out under stable condition.
The present invention is by the following technical solutions: a kind of lithium ion anode material, the oxide general formula is: xA
2OyM
2O
mZN
2O
N.Wherein A is an alkali metal, and M and N are selected from the metallic element among IIIB to VIIB, VIII, IIIA or the IVA in the periodic table of elements; X, y, z are respectively oxide A
2O, M
2O
mAnd N
2O
nMolal quantity; M and n are respectively the oxidation state of metallic element M and N; X=0.1～1.2, y=0.05～0.5, z=0.05～1.2, x/ (y+z)=0.35～1.2 is characterized in that: lithium ion anode material is made up of two dimension six side's layer structure crystal, the crystalline composite oxide of three-dimensional spinel structure or the vanadium oxide crystal of lithiumation.
The general formula of the present invention's two dimension six side's layer structure crystal is A
xMO
2, 0＜x＜1.1, and the derivative of doping or modification.
The general formula of the crystalline composite oxide of the three-dimensional spinel structure of the present invention is A
xMn
2-αM
αO
4, 0＜x＜1.1,0＜α＜2, and the derivative of doping or modification.
The vanadium oxide crystal of lithiumation of the present invention is Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13, and the derivative of doping or modification.
A kind of preparation method of lithium ion anode material, may further comprise the steps: one, airtight or have in the electrolysis synthesizer of hydrogen, nitrogen protection, direct electrolytic metal in containing the pure molten non-aqueous eletrolyte of organic additive, form the corresponding metal alkoxide, general formula is R-O-M, and wherein R is alkyl, alkoxyl or aryl radical; Two, metal alkoxide and contain the aqueous solution of the alkali metal salt or the alkali of auxiliary agent forms the sol precursor of positive electrode, and its general formula is xA
2OyM
2O
mZH
2O is partially crystallizable or complete unbodied hydrous oxide; Three, sol precursor removes solvent at 120 ℃ in 550 ℃, forms the Powdered presoma of positive electrode, and its general formula is xA
2OyM
2O
m, for the crystalline solid of high-sequential or contain the crystal of small amount of amorphous structure oxide; Four, Powdered presoma is in aerobic or oxygen-free atmosphere, and 450 ℃ to 960 ℃ solid phase reactions 0.5 to 48 hour obtain lithium ion anode material.
The solvent of the molten non-aqueous eletrolyte of the present invention's alcohol is the derivative of unitary fatty alcohol, binary aliphatic alcohol, multi-alcohol, phenol or phenol.
Additive of the present invention is the fatty alcohol, aliphatic acid, aromatic alcohol, aromatic acid, the derivative of aromatic acid, polymer, carbonic ester or the amino acid of aromatic acid of pure dissolubility;
The electrolyte of the molten electrolyte of the present invention's alcohol is anhydrous hydroxide, anhydrous halide, acetic anhydride salt, anhydrous nitrate, anhydrous perchlorate, anhydrous chlorate, anhydrous permanganate, anhydrous stibate, anhydrous chromic acid salt or the anhydrous bichromate of alkali metal lithium, sodium or potassium.
Electrolytical concentration is 0.05% to 45% in the molten non-aqueous eletrolyte of the present invention's alcohol.
Decomposition voltage is 2.0V to 50V between electrolytic anode of the present invention and negative electrode, and current strength is at 0.01A to 10A/cm
2Between.
Cathode material of the present invention is nickel, titanium or stainless steel, and anode can be a metal or alloy.
The concentration of metal alkoxide of the present invention is 0.5% to 45%.
The mol ratio of the metal of alkali metal and electrodissolution is in 0.1 to 1.3 scope in partially crystallizable of the present invention or the complete unbodied hydrous oxide.
Auxiliary agent of the present invention is inorganic compound and organic compound.
Inorganic compound of the present invention is carbonate or nitrate.
Organic compound of the present invention is the derivative of derivative, polymer, amino acid, cellulose, cellulosic derivative, catabolite or starch, catabolite or starch of derivative, polymer, aliphatic acid, the aliphatic acid of urea, monobasic or multi-alcohol, monobasic or multi-alcohol.
Sol precursor of the present invention remove solvent, can adopt spray drying, freeze drying, microwave drying or self-propagating high-temperature burning.
The grain Trail of the Powdered presoma powder of the present invention distributes and is between 0.01 μ m to the 3.5 μ m.
Solid phase reaction process of the present invention is divided into 5 steps or stage, 450 ℃～650 ℃ sintering 0.1～10 hour, 650 ℃～780 ℃ sintering 0.1～12 hour, 780 ℃～850 ℃ sintering 0.1～10 hour, 850 ℃～880 ℃ sintering 0.1～10 hour, 880 ℃～960 ℃ sintering 0.1～8 hour.
The present invention compared with prior art, lithium ion anode material is made up of two dimension six side's layer structure crystal, the crystalline composite oxide of three-dimensional spinel structure or the vanadium oxide crystal of lithiumation, monocrystal size in the particle is in 0.2 μ m～3.5 μ m, and particle size distribution is even; Crystalline phase purity height, no dephasign exists; Aspect electrical property, the initial capacity height of material.Adopting nonaqueous electrolytic solution, is electrolyte with the anhydrous alcohol solution, and what directly generate in electrolysis unit is metal alkoxide, as ethanol Cobalt, ethanol iron etc., itself and alcoholic solvent mutual solubility height, do not generate passivating film at electrode surface, do not have the accumulation of electronics and electric charge on the electrode, the current efficiency height of electrolytic process; It is constant that the conductance of electrolyte, solution viscosity keep substantially, and whole electrolytic process can carry out under stable electric current and polar plate voltage; Synthetic metal alkoxide and the alkali metal salt of electrolysis forms mixed uniformly colloidal sol, and follow-up solid phase reaction potential barrier is low, and the reaction the evolving path of reactant significantly reduces, and can shorten the solid phase reaction time significantly; The preparation technology's of metal alkoxide operability height is convenient to control the alkoxide that mixes of the multiple metal of synthetic various molar ratios, is easy to carry out the chemical doping and the physical doping of material, and surface modification treatment.
Description of drawings
Fig. 1 is the LiCoO that the embodiment of the invention 1 is synthesized
2XRD Spectrum figure.
Fig. 2 is the LiCoO that the embodiment of the invention 1 is synthesized
2The SEM shape appearance figure.
Fig. 3 is the LiCoO that the embodiment of the invention 2 is synthesized
2XRD Spectrum figure.
Fig. 4 is the LiCoO that the embodiment of the invention 2 is synthesized
2The SEM shape appearance figure.
Fig. 5 is the LiCoO that the embodiment of the invention 3 is synthesized
2XRD Spectrum figure.
Fig. 6 is the LiCoO that the embodiment of the invention 3 is synthesized
2The SEM shape appearance figure.
Fig. 7 is the LiCoO that the embodiment of the invention 4 is synthesized
2The XRD Spectrum figure of presoma.
Fig. 8 is the LiCoO that the embodiment of the invention 4 is synthesized
2The SEM shape appearance figure of presoma.
Fig. 9 is the LiCoO that the embodiment of the invention 4 is synthesized
2XRD Spectrum figure.
Figure 10 is the LiCoO that the embodiment of the invention 4 is synthesized
2The SEM shape appearance figure.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Lithium ion anode material of the present invention, composite oxides general formula are xA
2OyM
2O
mZN
2O
n, wherein M and N are selected from the IIIB～VIIB in the periodic table of elements, VIII, IIIA, the metallic element among the IVA; X, y, z are respectively oxide A
2O, M
2O
mAnd N
2O
nMolal quantity; M and n are respectively the oxidation state of metallic element M and N; X=0.1～1.2, y=0.05～0.5, z=0.05～1.2, x/ (y+z)=0.35～1.2.Composite oxides are at least by a kind of composition the in the derivative of the vanadium oxide of two dimension six side's layer structure crystal, three-dimensional spinel structure crystal, lithiumation and doping or modification.The oxide of wherein said six side's layer structure crystal is Li
xMO
2, 0＜x＜1.2, the oxide of spinel structure crystal is Li
xMn
2-αM
αO
4, 0＜x＜1.2,0≤α≤2, the vanadium oxide of lithiumation has Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13, its doping or modification derivative.
The preparation method of above-mentioned material may further comprise the steps: (1) is direct electrolytic metal in containing the alcoholic solution of organic additive, forms the corresponding metal alkoxide, and general formula is R-O-M.Wherein R is alkyl, alkoxyl or aryl radical, and M is at least the IIIB～VIIB in the periodic table of elements, VIII, IIIA, a kind of metallic element among the IVA;
(1) with metal alkoxide and the aqueous solution that contains the alkali metal compound of auxiliary agent, forms sol precursor xA
2OyM
2O
mZH
2O;
(2) sol precursor removes solvent, the Powdered presoma xA of formation positive electrode in 120 ℃～550 ℃
2OyM
2O
m
(3) Powdered presoma is in aerobic or oxygen-free atmosphere, in 450 ℃～960 ℃ solid phase reactions 0.5～48 hour, obtains target product.
The method for preparing lithium ion anode material that this patent invention proposes, according to following serial chemical reaction:
The ionization reaction of alcohol:
The reaction that takes place in the electrolysis unit:
Anode reaction:
Cathode reaction:
Overall reaction:
The reaction that takes place in the colloidal sol preparation process:
Hydrolysis:
Ion-exchange:
Interfacial Adsorption:
The reaction that takes place when colloidal sol dehydration or low-temperature heat:
Me is the metal of electrodissolution in the above chemical equation, Me (OH)
nBe the hydroxide sol of metal, R-OH is the absolute alcohol solvent, and R is alkyl, alkoxyl or aryl radical, and n is the oxidation state of metal ion.Me-OH and Me-O represent that respectively metal hydroxides or hydrous oxide can carry out the group and the surface activity adsorption potential of ion-exchange.MeO (OH)
N-2Be the hydroxy metal oxide, as MnO (OH)
2, MnO (OH), CoO (OH), NiO (OH) etc.
According to the chemical reaction that above the present invention follows, hydrogen ion and alkoxide ion (R-O that pure ionization produces
-), under the extra electric field effect, H
+Move and on negative electrode, form hydrogen to negative electrode, and R-O
-Then anode moves, near enrichment anode.The metal ion of anodic solution and alkoxide ion (R-O
-) form the metal alkoxide (R-O) of pure dissolubility
nMe.The hydrogen that negative electrode produces can also prevent that the steam in the surrounding environment from entering electrolyte as protective gas.
The present invention is the metal alkoxide M (O-R) that further improves alkali metal salt, electrolysis formation
nSolubility in non-aqueous eletrolyte guarantees the stable of electrolytic conductivity, and prevents the precipitate metal hydroxides that may occur, and adds some pure dissolubility organic additives in electrolyte, to promote the dissolving of inorganic metal salt, organic metal salt.The additive that the present invention chooses comprises aliphatic alcohol, aromatic alcohols, aliphatic carboxylic acid, aromatic carboxylic acid, phenol organic matter and amino acid and the corresponding derivative thereof of pure dissolubility, and the carbonic ester of strong polarity.More preferably a kind of in the derivative of ethylene glycol, glycerine or polymer, amino acid, the carbonic ester or several.Further preferred carbonic ester is ethylene carbonate EC and propylene carbonate ester PC.
Among the present invention, the auxiliary agent in the preparation sol precursor aqueous solution is inorganic matter and organic substance.Inorganic matter is carbonate and nitrate.Organic substance is a urea, water miscible aliphatic alcohol, aromatic alcohols, aliphatic carboxylic acid, aromatic carboxylic acid, amino acid and corresponding derivative or polymer, cellulose and derivative thereof and catabolite, starch and derivative thereof.These auxiliary agent compounds play a different role in the positive electrode building-up process.Inorganic compound is as precipitation reagent and perforating agent.Organic substance is as dispersant, perforating agent, template and combustion adjuvant.As template, hydroxide and hydrous oxide that precipitation and hydrolysis are produced are attached to organic compound by electrostatic attraction, reduce the inhomogeneities of reactant mixture.Promote reaction mass surface combustion ripple inwardly to transmit rapidly as combustion adjuvant, the self-propagating combustion reaction promptly takes place, can reduce reaction barrier, the accelerated reaction process.
The electrolysis unit of selecting for use among the present invention can prepare the metal alkoxide mixed solution continuously, and the mixed alcohol solvent can recycle.Electrolyte constantly circulates, and reaches reinforced solution and evenly distributes, and improves current efficiency.Decomposition voltage is 2.0V～50V between pole plate, and current strength is at 0.5A～10A/cm
2The concentration of metal alkoxide in electrolyte does not have limited, and the concentration of alkali metal salt is 0.5%～45% in the non-aqueous eletrolyte.By adjust size of current, polar board surface is long-pending and the electrodissolution amount of electrolysis time control transition metal.Voltage need be determined according to actual conditions between pole plate, as the resistance of electrolyte etc.
The positive electrode active materials that the present invention is fit to preparation comprises:
(1) by in the composite oxides of six side's layered crystal structures one or more, the anode material for lithium-ion batteries of composition.Monocrystalline oxide is Li
xMO
2, 0＜x＜1.2, M=Co, Ni, Mn etc., and it is carried out the Li of chemical doping
xCo
1-αM
αO
2, 0＜x＜1.2,0≤α≤1, M=Ni, Mn, Al, Cr, V etc.;
(2) any or several by in the spinel crystal structure composite oxides, the anode material for lithium-ion batteries of composition.Monocrystalline oxide is Li
xMn
2O
4And Li
xMn
2-αM
αO
4, 0≤α≤2, M=Co, Ni, Al, Cr, V etc.;
(3),, form the anode material for lithium-ion batteries that mixes with in the spinel crystal structure oxide one or more by in the composite oxides of six side's layered crystal structures one or more;
(4) by Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13, with and the derivative of modification or doping in one or more, the anode material for lithium-ion batteries of composition.
(5) by Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13, with and the derivative of modification or doping in one or more, with in the composite oxides of six side's layered crystal structures one or more, the anode material for lithium-ion batteries of composition.
(6) by Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13, with and the derivative of modification or doping in the composite oxides of one or more and spinel crystal structure in one or more, the anode material for lithium-ion batteries of composition.
(7) by Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13, with and the derivative of modification or doping in the composite oxides of one or more and spinel crystal structure in one or more, and with six side's layered crystal structure composite oxides in one or more, the anode material for lithium-ion batteries of composition.
The present invention is when the above anode material for lithium-ion batteries of preparation, and the raw material of employing is formed the following several situation that comprises:
(1) the synthetic metal alkoxide of electrolysis and the mixed alcohol solution of alkali metal salt mix hydrolysis formation sol precursor, the powder presoma of preparation with other anhydrous compound of pure dissolubility;
(2) the synthetic mixed metal alkoxide of electrolysis mixes with the alkali metal alcoholates of chemical synthesis, the synthetic sol precursor of hydrolysis in the aqueous solution, the powder presoma of preparation;
(3) metal hydroxides or the hydrous oxide powder that generate of the synthetic mixed metal alkoxide direct hydrolysis of electrolysis is with the mixture of alkali-metal salt or alkali;
(4) sol precursor of the synthetic metal alkoxide of one or more electrolysis mixes with one or more powder presomas and to size mixing the compound sol precursor of preparation;
(5) the different composition, the mixture of the various forms of powder presomas of different synthetic method preparations;
(6) layer structure monocrystalline, spinel structure monocrystalline, Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13With and the derivative monocrystalline of modification or doping in one or more, mix the reactant mixture of preparation with alkoxide;
(7) layer structure monocrystalline, spinel structure monocrystalline, Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13With and the derivative monocrystalline of modification or doping in one or more, evenly mix the reactant mixture of preparation with sol precursor;
(8) layer structure monocrystalline, spinel structure monocrystalline, Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13With and the derivative monocrystalline of modification or doping in one or more, evenly mix the reactant mixture of preparation with the powder presoma;
In the present invention, the preferred synthesis technique of the sol precursor of composite oxides:
(1) direct electrolytic metal in anhydrous alcohol solution, the alkoxide of formation metal ion evenly mixes with the aqueous solution of the alkali metal lithium salts that contains additive, and Separation of Solid and Liquid obtains sol precursor xLi
2OyM
2O
mZH
2O;
(2) sol precursor forms powder presoma xA in 350 ℃～650 ℃ dryings or low-temperature sintering 0.5～5 hour
2OyM
2O
m
(3) Powdered presoma is in oxygen-enriched atmosphere, and 650 ℃～950 ℃ solid phase reactions 0.5～48 hour obtain target product.
In a preferred embodiment of the invention, the Li of the preferred six side's layer structures of positive electrode
xMO
2LiMn with spinel structure
2One or both compositions among the O4 further are preferably LiCoO
2In a preferred embodiment of the invention, preferred anhydrous fatty alcohol of solvent or phenol organic matter, further preferred anhydrous monohydric alcohol.Additive in the electrolyte is preferably monobasic and multi-alcohol, phenol and carbonic ester.Further preferred organic substance is ethylene glycol, glycerine and carbonic ester.Carbonic ester is propylene carbonate ester PC more preferably.
In a preferred embodiment of the invention, in preparation sol precursor process, preferred carbonate of inorganic matter and nitrate in the selected auxiliary agent; Organic substance is preferably urea, aliphatic acid and its esters, cellulose and derivative thereof and catabolite, starch and derivative thereof.Further preferred inorganic is a carbonate, as lithium carbonate and lithium nitrate, and carbonic hydroammonium and ammonium carbonate.Preferred organic substance is amino acid, fatty alcohol and polymer thereof.
Embodiment 1
Cobalt piece with content 99.7% is an anode, and nonferrous metallurgy company in Jinchuan produces, and the high-quality stainless steel is done negative electrode, trade mark 310S, Switzerland produces, and the AR ethanol solution of AR lithium bromide is an electrolyte, consumption 100.0ml, wherein contain 2 gram LiBr, voltage across poles 5.5V, current density 1.0A/cm
2The area that the Cobalt piece immerses electrolyte is 2.5cm
2, obtain containing the electrolyte that ethanol Cobalt 10.6 restrains behind the electrolysis 100min.The LiOH of 30 milliliters of LITHIUM BATTERY and AR polyethylene glycol, the mixed aqueous solution of the degree of polymerization 1000, wherein contain anhydrous lithium hydroxide and polyethylene glycol and be respectively 2.9 grams and 10 grams, it is dropwise added the electrolyte that contains ethanol Cobalt under stirring condition, centrifuge model TGL-16C, Anting Scientific Instrument Factory, Shanghai makes isolated colloidal sol and puts into corundum crucible, in groom's stove, model SX-12-10, Chongming, Shanghai laboratory apparatus factory makes, in 550 ℃, 750 ℃, 850 ℃ and 920 ℃ are solid phase reaction 2.5 hours respectively, 1.5 hour, 6.5 hour and 2.5 hours, these four processes are carried out continuously, obtain LiCoO after the cooling
2Resistance is not less than 15M Ω, 60 ℃ of deionized waters, the excessive lithium in the washing by soaking product, and cleaning solution pH value is constant in 9.5, pHS-25, last Nereid section thunder magnetic manufactures a product, and filter cake was in 120 ℃ of vacuum dryings 2.0 hours, vacuum drying oven model D260, the manufacturing of Nantong county experiment Electric Applicance General Factory, the XRD Spectrum figure of corresponding powder, adopt D/Max2200PC, 3KW, Rigaku, with the SEM shape appearance figure, adopt JSM-6330F, JEOL sees Fig. 1 and Fig. 2 respectively.Embodiment 2
Cobalt piece with content 99.7% is an anode, and nonferrous metallurgy company in Jinchuan produces, and the high-quality stainless steel is done negative electrode, trade mark 310S, Switzerland produces, and the AR ethanol solution of AR sodium bromide is an electrolyte, consumption 100.0ml, wherein contain 2.0 gram NaBr, voltage across poles 6.5V, current density 1.0A/cm
2The area that the Cobalt piece immerses electrolyte is 2.5cm
2, obtain containing the electrolyte of 10.6 gram ethanol Cobalt behind the electrolysis 100min.30.0 the LiOH and the AR polyethylene glycol of milliliter LITHIUM BATTERY, the mixed aqueous solution of the degree of polymerization 1000, contain anhydrous lithium hydroxide and polyethylene glycol and be respectively 2.9 grams and 10.0 grams, it is dropwise added the electrolyte that contains ethanol Cobalt under stirring condition, centrifuge model TGL-16C, Anting Scientific Instrument Factory, Shanghai makes isolated colloidal sol and puts into corundum crucible, in groom's stove of blowing air stream, model SX-12-10, Chongming, Shanghai laboratory apparatus factory makes, earlier 150 ℃ of drying and dehydratings 20.0 minutes, afterwards at 550 ℃, 750 ℃, 850 ℃, 920 ℃ of solid phase reactions 1.5 hours respectively, 4.5 hour, 1.5 hour and 0.5 hour, these four processes are independently carried out respectively, and experience intensification-insulation-cooling separately obtains LiCoO
2, be not less than 15M Ω, 60 ℃ of deionized waters, the excessive lithium in the washing by soaking product with resistance, cleaning solution pH value is constant in 9.5, pHS-25, and last Nereid section thunder magnetic manufactures a product, filter cake is in 120 ℃ of vacuum dryings 2.0 hours, vacuum drying oven model D260, the manufacturing of Nantong county experiment Electric Applicance General Factory, the XRD Spectrum figure of corresponding powder adopts D/Max2200PC, 3KW, Rigaku and SEM shape appearance figure adopt JSM-6330F, JEOL sees Fig. 3 and Fig. 4 respectively.
Embodiment 3
Cobalt piece with content 99.7% is an anode, and nonferrous metallurgy company in Jinchuan produces, and the high-quality stainless steel is done negative electrode, trade mark 310S, Switzerland produces, and the AR ethanol solution of AR lithium bromide is an electrolyte, consumption 100.0ml, wherein contain 3.0 gram NaBr, voltage across poles 6.5V, current density 1.0A/cm
2The area that the Cobalt piece immerses electrolyte is 2.5cm
2, obtain containing the electrolyte that ethanol Cobalt 106.0 restrains behind the electrolysis 1000min.30.0 the LiOH and the AR polyethylene glycol of milliliter LITHIUM BATTERY, the mixed aqueous solution of the degree of polymerization 1000, contain anhydrous lithium hydroxide and polyethylene glycol and be respectively 9.0 grams and 12.0 grams, it is dropwise added the electrolyte that contains ethanol Cobalt under stirring condition, centrifuge model TGL-16C, Anting Scientific Instrument Factory, Shanghai makes, isolated colloidal sol is put into corundum crucible, microwave drying, adopt Panasonic's household microwave oven, power output 1000W is after 30 minutes, model SX-12-10 in groom's stove of blowing air stream, Chongming, Shanghai laboratory apparatus factory makes, and in 650 ℃ of solid phase reactions 1.5 hours, the cooling back was in 780 ℃ of reactions 8.5 hours, be warmed up to 920 ℃ of solid-phase sinterings 1.0 hours again, obtain LiCoO after the cooling
2, being not less than excessive lithium in 15M Ω, the 60 ℃ of deionized water washing by soaking products with resistance, cleaning solution pH value is constant in 9.5, pHS-25, last Nereid section thunder magnetic product, filter cake was in 120 ℃ of vacuum dryings 2.0 hours, vacuum drying oven model D260, the manufacturing of Nantong county experiment Electric Applicance General Factory, the XRD Spectrum figure D/Max2200PC of corresponding powder, 3KW, Rigaku, with SEM shape appearance figure JSM-6330F, JEOL sees Fig. 5 and Fig. 6 respectively.
Embodiment 4
Cobalt piece with content 99.7% is an anode, and nonferrous metallurgy company in Jinchuan produces, and the high-quality stainless steel is done negative electrode, trade mark 310S, Switzerland produces, and the AR ethanol solution of AR lithium bromide is an electrolyte, consumption 30ml, wherein contain 1 gram LiBr, voltage across poles 6.5V, current density 1.0A/cm
2The area that the Cobalt piece immerses electrolyte is 2.5cm
2, obtain containing the electrolyte that ethanol Cobalt 10.6 restrains behind the electrolysis 100min.The LiOH of 30 milliliters of LITHIUM BATTERY and AR polyethylene glycol, the mixed aqueous solution of the degree of polymerization 1000, contain anhydrous lithium hydroxide and polyethylene glycol and be respectively 2.9 grams and 10 grams, it is dropwise added the electrolyte that contains ethanol Cobalt under stirring condition, centrifuge model TGL-16C, Anting Scientific Instrument Factory, Shanghai makes isolated colloidal sol and puts into corundum crucible, model SX-12-10 in groom's stove, Chongming, Shanghai laboratory apparatus factory makes, and in 650 ℃ of drying and dehydratings, and combustion reaction 1.2 hours takes place, the XRD Spectrum figure D/Max2200PC of the corresponding powder of sample, 3KW, Rigaku and SEM shape appearance figure SM-6330F, JEOL sees Fig. 7 and Fig. 8 respectively.Sample after the burning is warming up to 900 ℃ of solid phase reactions again and obtained LiCoO in 2.0 hours in 750 ℃ of solid phase reactions 2.0 hours
2Be not less than excessive lithium in 15M Ω, the 60 ℃ of deionized water washing by soaking products with resistance, cleaning solution pH value is constant in 9.5, pHS-25, last Nereid section thunder magnetic product, filter cake was in 120 ℃ of vacuum dryings 2 hours, the XRD Spectrum figure D/Max2200PC of corresponding powder, 3KW, Rigaku and SEM shape appearance figure SM-6330F, JEOL sees Fig. 9 and Figure 10 respectively.
Claims (19)
1. lithium ion anode material, the oxide general formula is: xA
2OyM
2O
mZN
2O
n. wherein A is an alkali metal, and M and N are selected from the metallic element among IIIB to VIIB, VIII, IIIA or the IVA in the periodic table of elements; X, y, z are respectively oxide A
2O, M
2O
mAnd N
2O
nMolal quantity; M and n are respectively the oxidation state of metallic element M and N; X=0.1～1.2, y=0.05～0.5, z=0.05～1.2, x/ (y+z)=0.35～1.2 is characterized in that: lithium ion anode material is made up of two dimension six side's layer structure crystal, the crystalline composite oxide of three-dimensional spinel structure or the vanadium oxide crystal of lithiumation.
2. lithium ion anode material according to claim 1 is characterized in that: the general formula of described two-dimentional six side's layer structure crystal is A
xMO
2, 0＜x＜1.1, and the derivative of doping or modification.
3. lithium ion anode material according to claim 1 is characterized in that: the general formula of the crystalline composite oxide of described three-dimensional spinel structure is A
xMn
2-αM
αO
4, 0＜x＜1.1,0≤α≤2, and the derivative of doping or modification.
4. lithium ion anode material according to claim 1 is characterized in that: the vanadium oxide crystal of described lithiumation is Li
xV
2O
5, Li
xV
3O
8, Li
xV
6O
13, and the derivative of doping or modification.
5. the preparation method of a lithium ion anode material, may further comprise the steps: one, airtight or have in the electrolysis synthesizer of hydrogen, nitrogen protection, direct electrolytic metal in containing the pure molten non-aqueous eletrolyte of organic additive, form the corresponding metal alkoxide, general formula is R-O-M, and wherein R is alkyl, alkoxyl or aryl radical; Two, metal alkoxide and contain the aqueous solution of the alkali metal salt or the alkali of auxiliary agent forms the sol precursor of positive electrode, and its general formula is xA
2OyM
2O
mZH
2O is partially crystallizable or complete unbodied hydrous oxide; Three, sol precursor removes solvent at 120 ℃ in 550 ℃, forms the Powdered presoma of positive electrode, and its general formula is xA
2OyM
2O
m, for the crystalline solid of high-sequential or contain the crystal of small amount of amorphous structure oxide; Four, Powdered presoma is in aerobic or oxygen-free atmosphere, and 450 ℃ to 960 ℃ solid phase reactions 0.5 to 48 hour obtain lithium ion anode material.
6. the preparation method of lithium ion anode material according to claim 5, it is characterized in that: the solvent of the molten non-aqueous eletrolyte of described alcohol is the derivative of unitary fatty alcohol, binary aliphatic alcohol, multi-alcohol, phenol or phenol.
7. the preparation method of lithium ion anode material according to claim 5 is characterized in that: described additive is the fatty alcohol, aliphatic acid, aromatic alcohol, aromatic acid, the derivative of aromatic acid, polymer, carbonic ester or the amino acid of aromatic acid of pure dissolubility;
8. the preparation method of lithium ion anode material according to claim 5, it is characterized in that: the electrolyte of the molten electrolyte of described alcohol is the anhydrous hydroxide of alkali metal lithium, sodium or potassium, anhydrous halide, acetic anhydride salt, anhydrous nitrate, anhydrous perchlorate, anhydrous chlorate, anhydrous permanganate, anhydrous stibate, anhydrous chromic acid salt or anhydrous bichromate.
9. the preparation method of lithium ion anode material according to claim 5, it is characterized in that: electrolytical concentration is 0.05% to 45% in the molten non-aqueous eletrolyte of described alcohol.
10. the preparation method of lithium ion anode material according to claim 5, it is characterized in that: decomposition voltage is 2.0V to 50V between described electrolytic anode and negative electrode, and current strength is at 0.01A to 10A/cm
2Between.
11. the preparation method of lithium ion anode material according to claim 10 is characterized in that: described cathode material is nickel, titanium or stainless steel, and anode can be a metal or alloy.
12. the preparation method of lithium ion anode material according to claim 5 is characterized in that:
The concentration of described metal alkoxide is 0.5% to 45%.
13. the preparation method of lithium ion anode material according to claim 5 is characterized in that:
The mol ratio of the metal of alkali metal and electrodissolution is in 0.1 to 1.3 scope in described partially crystallizable or the complete unbodied hydrous oxide.
14. the preparation method of lithium ion anode material according to claim 5 is characterized in that:
Described auxiliary agent is inorganic compound and organic compound.
15. the preparation method of lithium ion anode material according to claim 14 is characterized in that: described inorganic compound is carbonate or nitrate.
16. the preparation method of lithium ion anode material according to claim 14 is characterized in that: described organic compound is the derivative of derivative, polymer, amino acid, cellulose, cellulosic derivative, catabolite or starch, catabolite or starch of derivative, polymer, aliphatic acid, the aliphatic acid of urea, monobasic or multi-alcohol, monobasic or multi-alcohol.
17. the preparation method of lithium ion anode material according to claim 5 is characterized in that:
Described sol precursor remove solvent, can adopt spray drying, freeze drying, microwave drying or self-propagating high-temperature burning.
18. the preparation method of lithium ion anode material according to claim 5 is characterized in that:
The grain Trail of described Powdered presoma powder distributes and is between 0.01 μ m to the 3.5 μ m.
19. the preparation method of lithium ion anode material according to claim 5 is characterized in that:
The solid phase reaction process is divided into 5 steps or stage, 450 ℃～650 ℃ sintering 0.1～10 hour, 650 ℃～780 ℃ sintering 0.1～12 hour, 780 ℃～850 ℃ sintering 0.1～10 hour, 850 ℃～880 ℃ sintering 0.1～10 hour, 880 ℃～960 ℃ sintering 0.1～8 hour.
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