CN104347853A - Lithium manganate composite positive electrode material, a preparing method thereof and a lithium-ion battery - Google Patents
Lithium manganate composite positive electrode material, a preparing method thereof and a lithium-ion battery Download PDFInfo
- Publication number
- CN104347853A CN104347853A CN201410491048.7A CN201410491048A CN104347853A CN 104347853 A CN104347853 A CN 104347853A CN 201410491048 A CN201410491048 A CN 201410491048A CN 104347853 A CN104347853 A CN 104347853A
- Authority
- CN
- China
- Prior art keywords
- lithium
- particularly preferably
- nitrate
- concentration gradient
- cobalt manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 44
- 239000011572 manganese Substances 0.000 claims abstract description 40
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 238000009768 microwave sintering Methods 0.000 claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- 239000010405 anode material Substances 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 27
- 239000000470 constituent Substances 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000011824 nuclear material Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 230000014759 maintenance of location Effects 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910013716 LiNi Inorganic materials 0.000 claims description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 235000019504 cigarettes Nutrition 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910015645 LiMn Inorganic materials 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000005121 nitriding Methods 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 238000010334 sieve classification Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 6
- 229940071264 lithium citrate Drugs 0.000 claims description 6
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 6
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- KKKAMDZVMJEEHQ-UHFFFAOYSA-N [Sn].[N+](=O)(O)[O-] Chemical compound [Sn].[N+](=O)(O)[O-] KKKAMDZVMJEEHQ-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 3
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ZYKTVIDNXTWTNS-UHFFFAOYSA-L [Co].[Mn].[Ni](O)O Chemical compound [Co].[Mn].[Ni](O)O ZYKTVIDNXTWTNS-UHFFFAOYSA-L 0.000 claims description 2
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 2
- 238000013467 fragmentation Methods 0.000 claims description 2
- 238000006062 fragmentation reaction Methods 0.000 claims description 2
- 238000000713 high-energy ball milling Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 229960001078 lithium Drugs 0.000 claims description 2
- 229940031993 lithium benzoate Drugs 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 239000012266 salt solution Substances 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 7
- 229910052596 spinel Inorganic materials 0.000 description 7
- 239000011029 spinel Substances 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 4
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910011681 LiNi0.7Co0.2Al0.1O2 Inorganic materials 0.000 description 2
- 229910015694 LiNi0.85Co0.1Al0.05O2 Inorganic materials 0.000 description 2
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- IWTZGPIJFJBSBX-UHFFFAOYSA-G aluminum;cobalt(2+);nickel(2+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Co+2].[Ni+2] IWTZGPIJFJBSBX-UHFFFAOYSA-G 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910000836 magnesium aluminium oxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/50—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
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- 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
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
Abstract
The invention provides a lithium manganate composite positive electrode material, a preparing method thereof and a lithium-ion battery. The composite positive electrode material is of a core-shell structure. The inner layer of the composite positive electrode material is an in-situ composite of lithium manganate and nickel-rich concentration gradient type nickel cobalt manganese/lithium aluminate LiMn2O4-LiNi1-x-yCox(Al/Mn)yO2, wherein x is more than 0 and less than or equal to 0.25, and y is more than 0 and less than or equal to 0.15; the outer shell of the composite positive electrode material is a metal oxide coated layer. According to the lithium manganate composite positive electrode material and the preparing method thereof, the in-situ composite of lithium manganate and nickel-rich concentration gradient type nickel cobalt manganese/lithium aluminate is obtained after in-site sintering of a manganese source, a nickel-rich concentration gradient type nickel cobalt manganese/lithium aluminate precursor, and a lithium source, then shell-layer metal oxide is cladded by using spray drying, and finally the composite positive electrode material is obtained by combining a microwave sintering process. The composite positive electrode material provided by the invention has relatively high specific capacity, and excellent high temperature cycling and storage performances.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to anode material for lithium-ion batteries and lithium ion battery technology of preparing, particularly a kind of lithium manganate composite anode material and by the lithium ion battery of this positive electrode as positive active material.
Background technology
The plurality of advantages such as lithium ion battery has that voltage is high, energy density is large, cyclicity is good, memory-less effect, self discharge are low, is widely used in fields such as portable power source, various portable electric appts, high-end number, electric automobiles.The performance of corresponding positive electrode to lithium ion battery plays decisive role, and all the time, exploitation electrochemical performance, have high power capacity, the positive electrode of good circulation performance is the study hotspot of lithium ion battery.
Lithium manganate having spinel structure belongs to cubic system, Fd3m space group, theoretical specific capacity is 148mAh/g, owing to having three-dimensional tunnel structure, lithium ion can reversibly deintercalation from spinel crystal lattice, can not cause subsiding of structure, thus having excellent high rate performance and stability, is one of more promising lithium ion anode material.Compare traditional positive electrodes such as cobalt acid lithium, the advantages such as LiMn2O4 has aboundresources, cost is low, pollution-free, fail safe is good, good rate capability, be desirable power battery anode material, but its poor cycle performance and electrochemical stability greatly limit its industrialization.The problems such as in charge and discharge process, especially when degree of depth discharge and recharge, still there is structural instability, capacity attenuation is fast, high temperature cyclic performance difference.Finishing and doping can effective its chemical properties of modification, and finishing can suppress dissolving and the electrolyte decomposition of manganese effectively.Doping effectively can suppress the Jahn-Teller effect in charge and discharge process.Finishing and doping are combined the chemical property that can improve material undoubtedly further, one of direction of from now on lithium manganate having spinel structure being carried out to study on the modification can be become.
In prior art, just normal employing solves the problem of the fast and poor high temperature stability of capacity attenuation to adulterate other metals and/or coated means of spinel lithium manganate.As, Chinese invention patent CN102324515B discloses a kind of lithium manganate having spinel structure preparation method and by its obtained LiMn2O4 and battery, first the compound of Li source compound, Mn oxide and doping metals M is mixed in dispersant, ball milling, drying, obtains the LiMn2O4 of doped metallic elements, and then carries out secondary ball milling mixing with aluminum phosphate through 500 ~ 1200 DEG C of calcining 10 ~ 50h, after 300 ~ 900 DEG C of calcining 5 ~ 30h, final acquisition is adulterated and coated manganate cathode material for lithium.According to the method for modifying that this patent provides, obtained battery first discharge specific capacity under 0.2C multiplying power is 110mAh/g, and first three time discharging efficiency is all greater than 96%, and 50 times circulation volume is 98.6% of first discharge specific capacity.But, although the doped metallic oxide that this patent provides and method for coating can improve the chemical property of LiMn2O4 to a certain extent, but the simple ball mill mixing method that adopts can cause doping and coated uneven problem, can further impact doping covered effect.Chinese invention patent CN1238260C provides a kind of preparation method of lithium ion accumulator positive electrode active material lithium manganate having spinel structure, by lithium carbonate and manganese dioxide micro mist and the metal oxide mixing and ball milling needing doping, first at 500 ~ 600 DEG C of pre-burning 10 ~ 15h, and then in 700 ~ 950 DEG C of calcining 10 ~ 30h, final acquisition target product, its first discharge specific capacity 112mAh/g, the capacitance loss rate after 50 times that circulates is 5%.Although the method obtains the modified effect of anticipation to a certain extent, have employed secondary clacining and not only increase energy consumption, the problem that doping is uneven can be there is equally.
Summary of the invention
The object of the present invention is to provide a kind of lithium manganate composite anode material, its preparation method and lithium ion battery, to solve the problem of cyclical stability difference under the fast and high temperature of lithium manganate having spinel structure capacity attenuation.
For achieving the above object, the technical solution adopted in the present invention is:
First, the invention provides a kind of lithium manganate composite anode material, this composite positive pole is nucleocapsid structure, and pattern is spherical or class is spherical, and internal layer is the In-situ reaction thing LiMn of LiMn2O4 and rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate
2o
4-LiNi
1-x-yco
x(Al/Mn)
yo
2, wherein, 0 < x≤0.25,0 < y≤0.15, rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate LiNi
1-x-yco
x(Al/Mn)
yo
2mass percentage be 0.1 ~ 20% of composite positive pole gross mass; Material shell is metal oxide coating layer, and the mass percentage of metal oxide coating layer is 0.05 ~ 10% of composite positive pole gross mass.
Preferably, described structural formula LiNi
1-x-yco
x(Al/Mn)
yo
2in, 0 < x≤0.22,0 < y≤0.12, is particularly preferably, 0 < x≤0.2,0 < y≤0.1;
Preferably, described rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate has nucleocapsid structure, and wherein, Ni concentration of element presents decline trend from internal granular layer to particle surface, in internal granular layer nuclear structure, Ni constituent content is the highest, and its mass percentage exceedes 60% of total content; Mn concentration of element presents increasing trend from internal granular layer to particle surface, and in particle outer shell nuclear structure, Mn constituent content is the highest, and its mass percentage exceedes 65% of total content; Further preferably, in described internal granular layer nuclear structure, Ni constituent content exceedes 65% of total content, and in particle outer shell nuclear structure, Mn constituent content exceedes 70% of total content; Particularly preferably, in described internal granular layer nuclear structure, Ni constituent content exceedes 70% of total content, and in particle outer shell nuclear structure, Mn constituent content exceedes 75% of total content;
Preferably, described rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate LiNi
1-x-yco
x(Al/Mn)
yo
2mass percentage be 0.3 ~ 15% of composite positive pole gross mass, more preferably 0.5 ~ 10%, be particularly preferably 1 ~ 5%;
Preferably, the mass percentage of described metal oxide coating layer is 0.1 ~ 8% of composite positive pole gross mass, more preferably 0.5 ~ 5%, be particularly preferably 1 ~ 3%.
Secondly, the invention provides a kind of preparation method of lithium manganate composite anode material, specifically comprise the following steps:
(1) the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate will be obtained after manganese source, rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate presoma and the calcining of lithium source original position;
(2) with the salpeter solution of 0.05 ~ 0.25mol/L, washing is carried out to above-mentioned compound and obtain inner nuclear material;
(3) described inner nuclear material to be added in metal salt solution obtained suspension-turbid liquid, spray-dried, microwave sintering, fragmentation sieves, obtain after classification the lithium manganate composite anode material of nucleocapsid structure.
Preferred as the inventive method, manganese source described in step (1) is the combination of a kind of in electrolytic manganese dioxide, mangano-manganic oxide, manganese carbonate or at least two kinds.
Preferred as the inventive method, rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate presoma described in step (1) comprises the combination of in nickelous carbonate cobalt manganese/aluminium presoma, nickel hydroxide cobalt manganese/aluminium presoma and cobalt nickel oxide manganses/aluminium a kind or at least two kinds;
Preferably, described rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate presoma has nucleocapsid structure, and wherein, Ni concentration of element presents decline trend from internal granular layer to particle surface, in internal granular layer nuclear structure, Ni constituent content is the highest, and its mass percentage exceedes 60% of total content; Mn concentration of element presents increasing trend from internal granular layer to particle surface, and in particle outer shell nuclear structure, Mn constituent content is the highest, and its mass percentage exceedes 65% of total content;
Further preferably, in described internal granular layer nuclear structure, Ni constituent content exceedes 65% of total content, and in particle outer shell nuclear structure, Mn constituent content exceedes 70% of total content;
Particularly preferably, in described internal granular layer nuclear structure, Ni constituent content exceedes 70% of total content, and in particle outer shell nuclear structure, Mn constituent content exceedes 75% of total content.
Preferred as the inventive method, lithium source described in step (1) is the combination of in lithium chloride, lithium bromide, lithium phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithium, lithium sulfate, lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, lithium benzoate and lithium citrate a kind or at least 2 kinds;
1 kind more preferably in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium formate, lithium citrate, tert-butyl alcohol lithium or the combination of at least 2 kinds;
Be particularly preferably the combination of in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium citrate a kind or at least 2 kinds.
Preferred as the inventive method, in step (1), to need manganese source, rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate presoma, lithium source, according to certain proportioning weigh batching, then to carry out ball milling or three-dimensional hybrid before calcination;
Preferably, described ball milling comprise in planetary type ball-milling, blue formula ball milling or high-energy ball milling any one, Ball-milling Time is 1 ~ 20h, more preferably 2 ~ 15h, is more preferably 3 ~ 10h;
Preferably, described three-dimensional hybrid adopts three-dimensional mixer, and incorporation time is 1 ~ 25h, more preferably 2 ~ 20h, is more preferably 3 ~ 15h.
Preferred as the inventive method, calcination process described in step (1) carries out in Muffle furnace, calcining heat is 650 ~ 1050 DEG C, calcination time 2 ~ 40h, then naturally cool to room temperature, after pulverizing, sieving, obtain the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate;
Preferably, described calcining heat is minimum is 650 DEG C, more preferably 700 ~ 1000 DEG C, is particularly preferably 750 ~ 950 DEG C;
Preferably, programming rate during described calcining is 1 ~ 15 DEG C/min, and more preferably 3 ~ 12 DEG C/min, is particularly preferably 5 ~ 10 DEG C/min;
Preferably, described calcination time at least 2h, more preferably 4 ~ 30h, is particularly preferably 6 ~ 25h;
Preferably, described calcining is carried out in an oxidizing atmosphere, carries out under being particularly preferably at least one atmosphere in air and oxygen atmosphere;
Preferably, the flow of described oxidizing atmosphere is 1 ~ 300ml/min, more preferably 5 ~ 250ml/min, is particularly preferably 10 ~ 200ml/min.
Preferred as the inventive method, step (2) specifically comprises: be added in described dilute nitric acid solution by the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate, through being uniformly mixed to obtain suspension-turbid liquid, described suspension-turbid liquid centrifugation, washing, drying, excessively sieve classification are obtained inner nuclear material;
Preferably, the concentration of described dilute nitric acid solution is at least 0.05mol/L, more preferably 0.08 ~ 0.2mol/L, is particularly preferably 0.1 ~ 0.15mol/L;
Preferably, in described washing process, solvent for use is deionized water, or any one or more than one the combination in deionized water and ethanol, propyl alcohol, glycerol and acetone;
Preferably, described drying is microwave drying, and described baking temperature is 80 ~ 250 DEG C, more preferably 90 ~ 200 DEG C, is particularly preferably 100 ~ 150 DEG C.
Preferred as the inventive method, the slaine described in step (3) is the combination of a kind of in cerous nitrate, nickel nitrate, zirconium nitrate, erbium nitrate, nitric acid molybdenum, aluminum nitrate, magnesium nitrate, butyl titanate, ammonium metavanadate, tetraethoxysilane, lanthanum nitrate, nitric acid tin, copper nitrate, zinc nitrate, yttrium nitrate and chromic nitrate or at least two kinds;
Preferably, described spraying dry adopts the one in centrifugal spray dryer, air flow type spray drying machine or pressure spray dryer, particularly preferably adopts centrifugal spray dryer;
Preferably, microwave sintering temperature is 250 ~ 750 DEG C, more preferably 300 ~ 700 DEG C, is particularly preferably 350 ~ 600 DEG C;
Preferably, the described microwave sintering time is 1 ~ 40h, more preferably 3 ~ 35h, is particularly preferably 5 ~ 25h.
Again, the present invention also provides a kind of lithium ion battery, and the positive active material of this battery comprises the lithium manganate composite anode material related in a kind of manganate cathode material for lithium provided by the present invention and the preparation method described in above-mentioned steps;
Preferred as the inventive method, above-mentioned lithium ion battery in the preparation process of anode pole piece using the product of discarded cigarette filter in ammonia after nitrogen treatment as carbon source;
Preferably, carbon source preparation method is, in ammonia atmosphere, carry out nitrogen treatment 1 ~ 5h by collecting the discarded cigarette filter come between 750 ~ 950 DEG C, programming rate remains on 1 ~ 15 DEG C/min, and acquisition has the nitrogenous material with carbon element of sub-hole and microcellular structure as carbon source;
Preferably, above-mentioned nitriding temperature is preferably 800 ~ 900 DEG C, and the nitrogen treatment time is preferably 1.5 ~ 4h, is particularly preferably 2 ~ 3h;
Preferably, programming rate is at least 1 DEG C/min, more preferably 3 ~ 10 DEG C/min, is particularly preferably 4 ~ 6 DEG C/min.
The lithium manganate composite anode material of manganate cathode material for lithium provided by the invention prepared by above-mentioned either a program, lithium ion battery prepared by described lithium manganate composite anode material first discharge specific capacity when 0.5C multiplying power is greater than 110mAh/g, first three time discharging efficiency is all greater than 98%, and the capability retention after 100 times that circulates is greater than 97.5%; The capability retention after 50 times that circulates when 55 DEG C is greater than 98.2%.
It is high that lithium manganate composite anode material described in arbitrary technique scheme provided by the invention and lithium ion battery have specific capacity, the outstanding advantages such as capacity attenuation is few, high temperature circulation good stability.Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention adopts the method for rich ni-type nickel cobalt manganese/aluminium presoma, Li source compound and the manganese source compound in-situ sintering with concentration gradient to complete the in-situ doped of rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate, improves specific capacity.
(2) coated slaine wiring solution-forming will be needed, the technique adopting spraying dry and microwave sintering to combine achieves the evenly coated of metal oxide on lithium manganate composite anode material surface, solves that manganate cathode material for lithium high temperature circulation is poor, specific capacity is low, decay the outstanding problem such as fast.
(3) before carrying out metallic element Surface coating, acidifying washing is carried out to lithium manganate composite anode material material, reduce the pH value of material surface, be conducive to the dispersiveness and the stability that improve slurry when preparing slurry, and then improve the high temperature circulation stability of battery.
(4) provided by the invention take lithium manganate composite anode material as the lithium ion battery of positive electrode active materials, in the preparation process of anode pole piece, adopt the nitrogenous material with carbon element of the sub-hole after discarded cigarette filter nitrogenize and microcellular structure as carbon source, while obtaining higher specific capacity and good multiplying power property, also achieve recycling of discarded object, there is good practical application and business promotion value.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail.It will be understood to those of skill in the art that following examples are only the preferred embodiments of the present invention, so that understand the present invention better, thus should not be considered as limiting scope of the present invention.For a person skilled in the art, the present invention can have various modifications and variations, within the spirit and principles in the present invention all, and any amendment made, equivalent replacement or improvement etc., all should be included within protection scope of the present invention.
Embodiment 1
Design is LiMn
2o
4-LiNi
0.65co
0.25mn
0.15o
2, wherein, rich nickel concentration gradient type nickle cobalt lithium manganate LiNi
0.65co
0.25mn
0.15o
2mass percentage be 15% of composite positive pole gross mass.By electrolytic manganese dioxide, rich nickel concentration gradient type nickelous carbonate cobalt manganese presoma and lithium hydroxide are according to aforementioned proportion weigh batching, adopt three-dimensional mixer mixing 1h, then in Muffle furnace, 8h are calcined in 850 DEG C, programming rate is 1 DEG C/min, whole calcination process is carry out in the oxygen atmosphere of 300ml/min at flow, naturally cool to room temperature, through pulverizing, the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickle cobalt lithium manganate is obtained after sieving, this compound is joined in the dilute nitric acid solution of 0.05mol/L and be uniformly mixed to obtain suspension-turbid liquid, through centrifugation, washing, 80 DEG C of microwave dryings, cross sieve classification and obtain inner nuclear material.This inner nuclear material is added obtained suspension-turbid liquid in the mixed solution of aluminum nitrate, magnesium nitrate and zirconium nitrate, aluminium oxide in final coating layer, magnesium oxide and zirconic gross mass is made to be 3% of composite positive pole gross mass, then spraying dry is carried out through centrifugal spray dryer, and in 750 DEG C of microwave sintering 1h, the final lithium manganate composite anode material obtaining nucleocapsid structure.
With above-mentioned composite material for positive active material, using the product of discarded cigarette filter in ammonia after nitrogen treatment, as carbon source, (the nitrogen treatment time is for 5h, nitriding temperature 750 DEG C, heating rate is 10 DEG C/min), find through test after making lithium ion battery, when 0.5C multiplying power, first discharge specific capacity is 112mAh/g, and first three time discharging efficiency is all greater than 98%, and the capability retention after 100 times that circulates is 98.1%; The capability retention after 50 times that circulates when 55 DEG C is 98.5%.
Embodiment 2
Design is LiMn
2o
4-LiNi
0.7co
0.2al
0.1o
2, wherein, rich nickel concentration gradient type nickel cobalt aluminic acid LiNi
0.7co
0.2al
0.1o
2mass percentage be 10% of composite positive pole gross mass.By electrolytic manganese dioxide, rich nickel concentration gradient type nickel cobalt aluminum hydroxide presoma and lithium hydroxide are according to aforementioned proportion weigh batching, adopt three-dimensional mixer mixing 10h, then in Muffle furnace, 15h are calcined in 800 DEG C, programming rate is 5 DEG C/min, whole calcination process is carry out in the oxygen atmosphere of 100ml/min at flow, naturally cool to room temperature, through pulverizing, the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickel cobalt lithium aluminate is obtained after sieving, this compound is joined in the dilute nitric acid solution of 0.2mol/L and be uniformly mixed to obtain suspension-turbid liquid, through centrifugation, washing, 250 DEG C of microwave dryings, cross sieve classification and obtain inner nuclear material.This inner nuclear material is added obtained suspension-turbid liquid in the mixed solution of chromic nitrate, ammonium metavanadate and nitric acid tin, the gross mass of chromium oxide, vanadium oxide and tin oxide in final coating layer is made to be 8% of composite positive pole gross mass, then spraying dry is carried out through centrifugal spray dryer, and in 650 DEG C of microwave sintering 10h, the final lithium manganate composite anode material obtaining nucleocapsid structure.
With above-mentioned composite material for positive active material, using the product of discarded cigarette filter in ammonia after nitrogen treatment, as carbon source, (the nitrogen treatment time is for 2h, nitriding temperature 900 DEG C, heating rate is 5 DEG C/min), find through test after making lithium ion battery, when 0.5C multiplying power, first discharge specific capacity is 116mAh/g, and first three time discharging efficiency is all greater than 98%, and the capability retention after 100 times that circulates is 98.5%; The capability retention after 50 times that circulates when 55 DEG C is 98.6%.
Embodiment 3
Design is LiMn
2o
4-LiNi
0.8co
0.15al
0.05o
2, wherein, rich nickel concentration gradient type nickel cobalt aluminic acid LiNi
0.8co
0.15al
0.05o
2mass percentage be 5% of composite positive pole gross mass.By electrolytic manganese dioxide, rich nickel concentration gradient type nickel cobalt aluminum hydroxide presoma and lithium hydroxide are according to aforementioned proportion weigh batching, with the mixture of deionized water and absolute ethyl alcohol for solvent ball milling 8h in high energy ball mill, then in Muffle furnace, 20h are calcined in 750 DEG C, programming rate is 10 DEG C/min, whole calcination process is carry out in the oxygen atmosphere of 150ml/min at flow, naturally cool to room temperature, through pulverizing, the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickel cobalt lithium aluminate is obtained after sieving, this compound is joined in the dilute nitric acid solution of 0.25mol/L and be uniformly mixed to obtain suspension-turbid liquid, through centrifugation, washing, 200 DEG C of microwave dryings, cross sieve classification and obtain inner nuclear material.This inner nuclear material is added obtained suspension-turbid liquid in the mixed solution of tetraethoxysilane and butyl titanate, the gross mass of silica and titanium oxide in final coating layer is made to be 5% of composite positive pole gross mass, then spraying dry is carried out through centrifugal spray dryer, and in 500 DEG C of microwave sintering 15h, the final lithium manganate composite anode material obtaining nucleocapsid structure.
With above-mentioned composite material for positive active material, using the product of discarded cigarette filter in ammonia after nitrogen treatment, as carbon source, (the nitrogen treatment time is for 1h, nitriding temperature 950 DEG C, heating rate is 1 DEG C/min), find through test after making lithium ion battery, when 0.5C multiplying power, first discharge specific capacity is 115mAh/g, and first three time discharging efficiency is all greater than 98%, and the capability retention after 100 times that circulates is 98.7%; The capability retention after 50 times that circulates when 55 DEG C is 98.5%.
Embodiment 4
Design is LiMn
2o
4-LiNi
0.85co
0.1mn
0.05o
2, wherein, rich nickel concentration gradient type nickel cobalt mangaic acid LiNi
0.85co
0.1mn
0.05o
2mass percentage be 1% of composite positive pole gross mass.By manganese nitrate, rich nickel concentration gradient type nickelous carbonate cobalt manganese presoma and lithium carbonate, lithium nitrate is according to aforementioned proportion weigh batching, with the mixture of deionized water and absolute ethyl alcohol for solvent ball milling 15h in high energy ball mill, then in Muffle furnace, 2h are calcined in 1050 DEG C, programming rate 3 DEG C/min, whole calcination process is carry out in the oxygen atmosphere of 50ml/min at flow, naturally cool to room temperature, through pulverizing, the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickle cobalt lithium manganate is obtained after sieving, this compound is joined in the dilute nitric acid solution of 0.05mol/L and be uniformly mixed to obtain suspension-turbid liquid, through centrifugation, washing, 120 DEG C of microwave dryings, cross sieve classification and obtain inner nuclear material.This inner nuclear material is added obtained suspension-turbid liquid in ammonium metavanadate solution, the gross mass of silica and titanium oxide in final coating layer is made to be 0.3% of composite positive pole gross mass, then spraying dry is carried out through centrifugal spray dryer, and in 250 DEG C of microwave sintering 20h, the final lithium manganate composite anode material obtaining nucleocapsid structure.
With above-mentioned composite material for positive active material, using the product of discarded cigarette filter in ammonia after nitrogen treatment, as carbon source, (the nitrogen treatment time is for 3h, nitriding temperature 800 DEG C, heating rate is 6 DEG C/min), find through test after making lithium ion battery, when 0.5C multiplying power, first discharge specific capacity is 111.5mAh/g, and first three time discharging efficiency is all greater than 98%, and the capability retention after 100 times that circulates is 98%; The capability retention after 50 times that circulates when 55 DEG C is 98.3%.
Embodiment 5
Design is LiMn
2o
4-LiNi
0.85co
0.1al
0.05o
2, wherein, rich nickel concentration gradient type nickel cobalt aluminic acid LiNi
0.85co
0.1al
0.05o
2mass percentage be 3% of composite positive pole gross mass.By mangano-manganic oxide, rich nickel concentration gradient type nickelous carbonate cobalt aluminium presoma and lithium hydroxide, lithium acetate is according to aforementioned proportion weigh batching, adopt three-dimensional mixer mixing 15h, then in Muffle furnace, 6h are calcined in 900 DEG C, programming rate 6 DEG C/min, whole calcination process is carry out in the air atmosphere of 120ml/min at flow, naturally cool to room temperature, through pulverizing, the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickel cobalt lithium aluminate is obtained after sieving, this compound is joined in the dilute nitric acid solution of 0.1mol/L and be uniformly mixed to obtain suspension-turbid liquid, through centrifugation, washing, 150 DEG C of microwave dryings, cross sieve classification and obtain inner nuclear material.This inner nuclear material is added obtained suspension-turbid liquid in the mixed solution of lanthanum nitrate, cerous nitrate and nitric acid molybdenum, the gross mass of lanthana, cerium oxide and molybdenum oxide in final coating layer is made to be 2% of composite positive pole gross mass, then spraying dry is carried out through centrifugal spray dryer, and in 550 DEG C of microwave sintering 12h, the final lithium manganate composite anode material obtaining nucleocapsid structure.
With above-mentioned composite material for positive active material, using the product of discarded cigarette filter in ammonia after nitrogen treatment, as carbon source, (the nitrogen treatment time is for 2h, nitriding temperature 880 DEG C, heating rate is 5 DEG C/min), find through test after making lithium ion battery, when 0.5C multiplying power, first discharge specific capacity is 114.2mAh/g, and first three time discharging efficiency is all greater than 98%, and the capability retention after 100 times that circulates is 98.3%; The capability retention after 50 times that circulates when 55 DEG C is 98.5%.
Embodiment 6
Design is LiMn
2o
4-LiNi
0.8co
0.1mn
0.1o
2, wherein, rich nickel concentration gradient type nickel cobalt mangaic acid LiNi
0.8co
0.1mn
0.1o
2mass percentage be 2% of composite positive pole gross mass.By electrolytic manganese dioxide, rich nickel concentration gradient type nickelous carbonate cobalt manganese presoma and lithium hydroxide are according to aforementioned proportion weigh batching, adopt three-dimensional mixer mixing 12h, then in Muffle furnace, 4h are calcined in 1000 DEG C, programming rate 5 DEG C/min, whole calcination process is carry out in the air atmosphere of 150ml/min at flow, naturally cool to room temperature, through pulverizing, the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickle cobalt lithium manganate is obtained after sieving, this compound is joined in the dilute nitric acid solution of 0.05mol/L and be uniformly mixed to obtain suspension-turbid liquid, through centrifugation, washing, 200 DEG C of microwave dryings, cross sieve classification and obtain inner nuclear material.This inner nuclear material is added obtained suspension-turbid liquid in the mixed solution of aluminum nitrate and magnesium nitrate, aluminium oxide and magnesian gross mass in final coating layer is made to be 1% of composite positive pole gross mass, then spraying dry is carried out through centrifugal spray dryer, and in 450 DEG C of microwave sintering 16h, the final lithium manganate composite anode material obtaining nucleocapsid structure.
With above-mentioned composite material for positive active material, using the product of discarded cigarette filter in ammonia after nitrogen treatment, as carbon source, (the nitrogen treatment time is for 1.5h, nitriding temperature 900 DEG C, heating rate is 3 DEG C/min), find through test after making lithium ion battery, when 0.5C multiplying power, first discharge specific capacity is 116.3mAh/g, and first three time discharging efficiency is all greater than 98%, and the capability retention after 100 times that circulates is 98.4%; The capability retention after 50 times that circulates when 55 DEG C is 98.6%.
Claims (12)
1. a lithium manganate composite anode material, is characterized in that, described composite positive pole is nucleocapsid structure, and pattern is spherical or class is spherical, and internal layer is the In-situ reaction thing LiMn of LiMn2O4 and rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate
2o
4-LiNi
1-x-yco
x(Al/Mn)
yo
2, wherein 0 < x≤0.25,0 < y≤0.15, rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate LiNi
1-x-yco
x(Al/Mn)
yo
2mass percentage be 0.1 ~ 20% of composite positive pole gross mass; Material shell is metal oxide coating layer, and the mass percentage of metal oxide coating layer is 0.05 ~ 10% of composite positive pole gross mass.
Preferably, described structural formula LiNi
1-x-yco
x(Al/Mn)
yo
2in, 0 < x≤0.22,0 < y≤0.12, is particularly preferably, 0 < x≤0.2,0 < y≤0.1;
Preferably, described rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate has nucleocapsid structure, and wherein, Ni concentration of element presents decline trend from internal granular layer to particle surface, in internal granular layer nuclear structure, Ni constituent content is the highest, and its mass percentage exceedes 60% of total content; Mn concentration of element presents increasing trend from internal granular layer to particle surface, and in particle outer shell nuclear structure, Mn constituent content is the highest, and its mass percentage exceedes 65% of total content; Further preferably, in described internal granular layer nuclear structure, Ni constituent content exceedes 65% of total content, and in particle outer shell nuclear structure, Mn constituent content exceedes 70% of total content; Particularly preferably, in described internal granular layer nuclear structure, Ni constituent content exceedes 70% of total content, and in particle outer shell nuclear structure, Mn constituent content exceedes 75% of total content;
Preferably, described rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate LiNi
1-x-yco
x(Al/Mn)
yo
2mass percentage be 0.3 ~ 15% of composite positive pole gross mass, more preferably 0.5 ~ 10%, be particularly preferably 1 ~ 5%;
Preferably, the mass percentage of described metal oxide coating layer is 0.1 ~ 8% of composite positive pole gross mass, more preferably 0.5 ~ 5%, be particularly preferably 1 ~ 3%.
2. a preparation method for a kind of lithium manganate composite anode material as claimed in claim 1, comprises the following steps:
(1) the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate will be obtained after manganese source, rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate presoma and the calcining of lithium source original position;
(2) with the salpeter solution of 0.05 ~ 0.25mol/L, washing is carried out to above-mentioned compound and obtain inner nuclear material;
(3) described inner nuclear material to be added in metal salt solution obtained suspension-turbid liquid, spray-dried, microwave sintering, fragmentation sieves, obtain after classification the lithium manganate composite anode material of nucleocapsid structure.
3. preparation method according to claim 2, is characterized in that, manganese source described in step (1) is the combination of a kind of in electrolytic manganese dioxide, mangano-manganic oxide, manganese carbonate or at least two kinds.
4. preparation method according to claim 2, it is characterized in that, rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate presoma described in step (1) comprises the combination of in nickelous carbonate cobalt manganese/aluminium presoma, nickel hydroxide cobalt manganese/aluminium presoma and cobalt nickel oxide manganses/aluminium a kind or at least two kinds;
Preferably, described rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate presoma has nucleocapsid structure, and wherein, Ni concentration of element presents decline trend from internal granular layer to particle surface, in internal granular layer nuclear structure, Ni constituent content is the highest, and its mass percentage exceedes 60% of total content; Mn concentration of element presents increasing trend from internal granular layer to particle surface, and in particle outer shell nuclear structure, Mn constituent content is the highest, and its mass percentage exceedes 65% of total content;
Further preferably, in described internal granular layer nuclear structure, Ni constituent content exceedes 65% of total content, and in particle outer shell nuclear structure, Mn constituent content exceedes 70% of total content;
Particularly preferably, in described internal granular layer nuclear structure, Ni constituent content exceedes 70% of total content, and in particle outer shell nuclear structure, Mn constituent content exceedes 75% of total content.
5. preparation method according to claim 2, it is characterized in that, lithium source described in step (1) is the combination of in lithium chloride, lithium bromide, lithium phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithium, lithium sulfate, lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, lithium benzoate and lithium citrate a kind or at least 2 kinds;
1 kind more preferably in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium formate, lithium citrate, tert-butyl alcohol lithium or the combination of at least 2 kinds;
Be particularly preferably the combination of in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium citrate a kind or at least 2 kinds.
6. preparation method according to claim 2, it is characterized in that, in step (1), to need manganese source, rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate presoma, lithium source before calcination, according to certain proportioning weigh batching, then to carry out ball milling or three-dimensional hybrid;
Preferably, described ball milling comprise in planetary type ball-milling, blue formula ball milling or high-energy ball milling any one, Ball-milling Time is 1 ~ 20h, more preferably 2 ~ 15h, is more preferably 3 ~ 10h;
Preferably, described three-dimensional hybrid adopts three-dimensional mixer, and incorporation time is 1 ~ 25h, more preferably 2 ~ 20h, is more preferably 3 ~ 15h.
7. preparation method according to claim 2, it is characterized in that, calcination process described in step (1) carries out in Muffle furnace, calcining heat is 650 ~ 1050 DEG C, calcination time 2 ~ 40h, then naturally cool to room temperature, after pulverizing, sieving, obtain the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate;
Preferably, described calcining heat is minimum is 650 DEG C, more preferably 700 ~ 1000 DEG C, is particularly preferably 750 ~ 950 DEG C;
Preferably, programming rate during described calcining is 1 ~ 15 DEG C/min, and more preferably 3 ~ 12 DEG C/min, is particularly preferably 5 ~ 10 DEG C/min;
Preferably, described calcination time at least 2h, more preferably 4 ~ 30h, is particularly preferably 6 ~ 25h;
Preferably, described calcining is carried out in an oxidizing atmosphere, carries out under being particularly preferably at least one atmosphere in air and oxygen atmosphere;
Preferably, the flow of described oxidizing atmosphere is 1 ~ 300ml/min, more preferably 5 ~ 250ml/min, is particularly preferably 10 ~ 200ml/min.
8. preparation method according to claim 2, it is characterized in that, step (2) specifically comprises: be added in described dilute nitric acid solution by the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate, through being uniformly mixed to obtain suspension-turbid liquid, described suspension-turbid liquid centrifugation, washing, drying, excessively sieve classification are obtained inner nuclear material;
Preferably, the concentration of described dilute nitric acid solution is at least 0.05mol/L, more preferably 0.08 ~ 0.2mol/L, is particularly preferably 0.1 ~ 0.15mol/L;
Preferably, in described washing process, solvent for use is deionized water, or any one or more than one the combination in deionized water and ethanol, propyl alcohol, glycerol and acetone;
Preferably, described drying is microwave drying, and described baking temperature is 80 ~ 250 DEG C, more preferably 90 ~ 200 DEG C, is particularly preferably 100 ~ 150 DEG C.
9. the preparation method according to any one in claim 2 ~ 8, it is characterized in that, the slaine described in step (3) is the combination of a kind of in cerous nitrate, nickel nitrate, zirconium nitrate, erbium nitrate, nitric acid molybdenum, aluminum nitrate, magnesium nitrate, butyl titanate, ammonium metavanadate, tetraethoxysilane, lanthanum nitrate, nitric acid tin, copper nitrate, zinc nitrate, yttrium nitrate and chromic nitrate or at least two kinds;
Preferably, described spraying dry adopts the one in centrifugal spray dryer, air flow type spray drying machine or pressure spray dryer, particularly preferably adopts centrifugal spray dryer;
Preferably, microwave sintering temperature is 250 ~ 750 DEG C, more preferably 300 ~ 700 DEG C, is particularly preferably 350 ~ 600 DEG C;
Preferably, the described microwave sintering time is 1 ~ 40h, more preferably 3 ~ 35h, is particularly preferably 5 ~ 25h.
10. preparation method according to claims 2 to 9, it is characterized in that, described lithium ion battery comprise with claim 1 or the preparation method according to any one of claim 1 ~ 9 the lithium manganate composite anode material that the obtains lithium ion battery that is positive active material.
11. 1 kinds of lithium ion batteries, is characterized in that, described anode slice of lithium ion battery in preparation process using the product of discarded cigarette filter in ammonia after nitrogen treatment as carbon source;
Further, carbon source preparation method is, in ammonia atmosphere, carry out nitrogen treatment 1 ~ 5h by collecting the discarded cigarette filter come between 750 ~ 950 DEG C, programming rate remains on 1 ~ 15 DEG C/min, and acquisition has the nitrogenous material with carbon element of sub-hole and microcellular structure as carbon source;
Further, above-mentioned nitriding temperature is preferably 800 ~ 900 DEG C, and the nitrogen treatment time is preferably 1.5 ~ 4h, is particularly preferably 2 ~ 3h;
Further, programming rate is at least 1 DEG C/min, more preferably 3 ~ 10 DEG C/min, is particularly preferably 4 ~ 6 DEG C/min.
12. according to a kind of lithium manganate composite anode material, its preparation method and the lithium ion battery described in claim 1 ~ 11, it is characterized in that, lithium ion battery prepared by described lithium manganate composite anode material first discharge specific capacity when 0.5C multiplying power is greater than 110mAh/g, first three time discharging efficiency is all greater than 98%, and the capability retention after 100 times that circulates is greater than 97.5%; The capability retention after 50 times that circulates when 55 DEG C is greater than 98.2%.
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