CN113046819A - Preparation method of monocrystalline lithium manganate, monocrystalline lithium manganate and application thereof - Google Patents
Preparation method of monocrystalline lithium manganate, monocrystalline lithium manganate and application thereof Download PDFInfo
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- CN113046819A CN113046819A CN202110254922.5A CN202110254922A CN113046819A CN 113046819 A CN113046819 A CN 113046819A CN 202110254922 A CN202110254922 A CN 202110254922A CN 113046819 A CN113046819 A CN 113046819A
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- Prior art keywords
- lithium manganate
- crystal
- manganese
- lithium
- precursor
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Links
- 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 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 164
- 239000002243 precursor Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 37
- 150000002696 manganese Chemical class 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- 239000007790 solid phase Substances 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 50
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 45
- 229910052748 manganese Inorganic materials 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 8
- 239000001433 sodium tartrate Substances 0.000 claims description 8
- 229960002167 sodium tartrate Drugs 0.000 claims description 8
- 235000011004 sodium tartrates Nutrition 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 7
- 229910052693 Europium Inorganic materials 0.000 claims description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 7
- 229910052689 Holmium Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- 229910052772 Samarium Inorganic materials 0.000 claims description 7
- 229910052771 Terbium Inorganic materials 0.000 claims description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052706 scandium Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 5
- 230000000536 complexating effect Effects 0.000 claims description 5
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 4
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 239000011564 manganese citrate Substances 0.000 claims description 3
- 235000014872 manganese citrate Nutrition 0.000 claims description 3
- 229940097206 manganese citrate Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 150000005323 carbonate salts Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims 1
- 230000006872 improvement Effects 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 2
- 238000005056 compaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000003792 electrolyte Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000012071 phase Substances 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000411 inducer Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- XXYBORWFPQAJKV-UHFFFAOYSA-K manganese(3+);carbonate;hydroxide Chemical compound [OH-].[Mn+3].[O-]C([O-])=O XXYBORWFPQAJKV-UHFFFAOYSA-K 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
-
- 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
- H01M4/36—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
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention belongs to the technical field of material synthesis, and particularly relates to a preparation method of single crystal lithium manganate, which comprises the following steps: s1, crystallizing soluble manganese salt, alkali liquor, soluble carbonate and a complexing agent through a complex reaction, and performing high-temperature treatment after precipitation and aging to obtain a manganese-series single crystal precursor with controllable particle size distribution; s2, mixing the manganese series single crystal precursor with a lithium source to obtain a mixture; and S3, heating the mixture in air or oxidizing atmosphere to carry out solid-phase sintering reaction to obtain the single-crystal lithium manganate with controllable particle size, wherein the shape of the obtained single-crystal lithium manganate is almost kept, and the particle size of the obtained single-crystal lithium manganate is controllable. In addition, the invention also relates to single-crystal lithium manganate and application thereof in a lithium ion battery. Compared with the prior art, the single-crystal lithium manganate prepared by the method has the advantages of small specific surface area, high solid content of slurry, high pole piece compaction density and improvement on the performance of a lithium manganate material.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a preparation method of single-crystal lithium manganate, single-crystal lithium manganate and application of single-crystal lithium manganate.
Background
The spinel type lithium manganate serving as the lithium ion battery anode material has the characteristics of higher charge-discharge voltage platform, excellent rate capability and the like. Meanwhile, because the manganese ore resource is rich, the lithium manganate synthesis technology is not complex, and the cost of the lithium manganate anode material is low, the lithium manganate anode material has wide market space in the lithium ion battery subdivision field sensitive to the battery cost.
However, the lithium ion battery prepared from the lithium manganate cathode material synthesized by the conventional method and process has faster capacity fading in the actual charging/discharging process, and the capacity fading trend is further enhanced at higher temperature. In summary, the reason why the capacity of the lithium ion battery prepared from the lithium manganate cathode material decays rapidly in actual work can be summarized as follows: (1) during the charge/discharge process of lithium manganate, John-Teller phase transformation (the material structure is irreversibly changed from a cubic phase with electrochemical activity to a tetragonal phase with electrochemical inertia) easily occurs, so that capacity attenuation is caused; (2) mn of lithium manganate positive electrode in circulation process3+Mn produced by disproportionation of ions2+Dissolved into the electrolyte and transferred and deposited on the negative electrode SEI film, resulting in the occurrence of a lithium ion trapping region on the SEI film that consumes a large amount of lithium ions and thus capacity fading. This process occurs more readily at high temperatures; (3) the dissolution of Mn ions generates oxygen defects caused by structural oxygen loss in the lithium manganate material, so that the crystal structure is no longer electrochemically active, and Mn generated by the process4+The high oxidation property of (2) also causes decomposition of the electrolyte. Therefore, better performance is to be obtainedThe lithium manganate material is an effective method for inhibiting John-Teller phase transformation and Mn ion dissolution problems by improving the stability of the material structure in the charging/discharging process.
At present, a large number of documents report that a mode of doping other elements (such as Ti, W, Al, etc.) in a bulk phase is adopted in a lithium manganate synthesis process, so that Jahn-Teller phase transformation in a lithium manganate de-intercalation/deintercalation process can be inhibited, and the cycle stability of a lithium manganate material is improved in a way of improving the structural stability of the lithium manganate material, and related chinese patents are published (see CN110336016A and CN 108206275A). In addition, impurity elements doped in the bulk phase also have the function of inhibiting the growth of a (111) plane in the growth process of lithium manganate crystal grains. Research shows that the reduction of the contact of the (111) crystal face and the electrolyte is beneficial to inhibiting the dissolution phenomenon of Mn in the electrolyte. The purpose of preventing the lithium manganate from directly contacting with the electrolyte can be realized by directly coating the lithium manganate crystal particles with the metal oxide, so that the dissolution phenomenon of manganese ions at a solid-liquid interface in the electrolyte is reduced, and the performance of the lithium manganate material is improved (see Chinese patents CN102694167B and CN 102569807B). The bulk phase doping and surface coating methods can be combined, and the performance of the lithium manganate material can be improved by simultaneously improving the structural stability of the lithium manganate and reducing the contact area of lithium manganate crystal particles and electrolyte (for example, published Chinese patent CN 109216694A).
In addition, a smaller specific surface area is obtained by preparing the single-crystal lithium manganate, and the purpose of reducing the contact area of the lithium manganate material and the electrolyte can be achieved. And the specific surface area of the lithium manganate can be regulated and controlled by controlling the size of the lithium manganate single crystal. However, when the lithium manganate single crystal is prepared, the spinel type lithium manganate single crystal prepared by the common solid-phase reaction is octahedral in appearance and has obvious (111) crystal faces, and a large number of exposed (111) crystal faces are directly contacted with an electrolyte, so that Mn is greatly dissolved in the electrolyte in the charging and discharging processes.
In view of the above, it is necessary to provide a technical solution to solve the above technical problems.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the method for preparing the single-crystal lithium manganate by preparing the single-crystal manganese precursor is provided, the irregular single-crystal lithium manganate with non-octahedral appearance is prepared, and the performance of the lithium manganate material is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of single crystal lithium manganate comprises the following steps:
s1, crystallizing the soluble manganese salt, the alkali liquor, the soluble carbonate and the complexing agent through a complex reaction to obtain a manganese series single crystal precursor with controllable particle size distribution;
s2, mixing the manganese series single crystal precursor with a lithium source to obtain a mixture;
and S3, heating the mixture in air or oxidizing atmosphere to carry out solid-phase sintering reaction to obtain the single-crystal lithium manganate with controllable particle size.
As an improvement of the method for preparing single-crystal lithium manganate of the present invention, in S1, the soluble manganese salt includes at least one of manganese sulfate, manganese chloride, manganese nitrate, manganese citrate and manganese acetate, the alkali solution includes at least one of sodium hydroxide, potassium hydroxide and ammonia water, the soluble carbonate includes at least one of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate, and the complexing agent includes at least one of ammonia water, ammonium salt, sodium tartrate, disodium ethylenediaminetetraacetate and citric acid.
As an improvement of the preparation method of the single-crystal lithium manganate, in S1, the manganese single-crystal precursor is prepared by a precipitation method, a mixed solvent method or a hydrothermal method. Preferably, the manganese series single crystal precursor is prepared by a liquid phase method.
As an improvement of the preparation method of the single crystal lithium manganate of the present invention, in S2, the manganese single crystal precursor and the lithium source are directly mixed and then uniformly mixed to obtain the mixture; or adding a solvent into the manganese series single crystal precursor and the lithium source, uniformly mixing and drying to obtain the mixture. Preferably, the manganese single crystal precursor and the lithium source are directly mixed and then uniformly mixed by a mechanical method. Or dissolving the manganese series single crystal precursor and the lithium source in a solvent, mechanically stirring, uniformly mixing and drying.
As an improvement of the method for preparing single-crystal lithium manganate according to the present invention, in S2, the lithium source includes at least one of lithium oxide, lithium carbonate, lithium nitrate, lithium acetate and lithium hydroxide.
As an improvement of the method for preparing single-crystal lithium manganate according to the present invention, in S3, the solid-phase sintering reaction comprises a first sintering, and the first sintering comprises the following step-wise heating operations:
1) heating to 450-700 ℃ at the speed of 2-20 ℃/min, and preserving heat for 4-24 h;
2) heating to 750-950 ℃ at the speed of 2-20 ℃/min, and preserving heat for 4-30 h.
As an improvement of the preparation method of the single-crystal lithium manganate, in the step 1), the heating time is at least 4 h; in the step 2), the heating time is 4-30 h.
As an improvement of the method for preparing single-crystal lithium manganate of the present invention, in S3, the solid-phase sintering reaction further comprises cooling the product obtained by the first sintering, grinding or pulverizing, and then sintering again.
As an improvement of the preparation method of the single-crystal lithium manganate of the present invention, in S1, doping substances are added to the soluble manganese salt, the alkali solution, the soluble carbonate and the complexing agent to perform a complexing reaction;
the doping material comprises at least one of oxide, inorganic salt and organic salt, and contains an element M, wherein the element M is at least one of Li, Ti, Zr, La, Al, Ce, Sr, Pr, Nd, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Sb, Mg, Tm, Bi, Mo, Sn, Zn, V, W, Yb, Lu, B, Y and Sc; the ratio of the total substance quantity of the element M in the single-crystal lithium manganate to the substance quantity of the manganese element in the manganese series single-crystal precursor is 1: (10-1000). The impurity type and content in the precursor can be regulated and controlled in the process of preparing the manganese-based single crystal precursor, and the manganese-based single crystal precursor is subjected to homogeneous doping in the process of forming a single crystal by adding the dopant.
As an improvement of the method for preparing single crystal lithium manganate of the present invention, in S1, the method further comprises coating the surface of the manganese-based single crystal precursor with a coating substance;
the coating material comprises at least one of oxide, inorganic salt and organic salt, the coating material contains an element M, the element M is at least one of Li, Ti, Zr, La, Al, Ce, Sr, Pr, Nd, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Sb, Mg, Tm, Bi, Mo, Sn, Zn, V, W, Yb, Lu, B, Y and Sc, and the ratio of the total substance amount of the element M in the single-crystal lithium manganate to the substance amount of the manganese element in the surface-coated manganese single-crystal precursor is 1: (10-1000). The surface of the manganese series single crystal precursor is coated, and the single crystal lithium manganate with doping elements distributed in a gradient manner from the surface to the inside can be formed.
As an improvement of the preparation method of the single crystal lithium manganate, in S1, after the surface of the manganese series single crystal precursor is coated with a coating substance, the preparation method further comprises a pretreatment operation, wherein the pretreatment operation comprises drying the manganese series single crystal precursor coated on the surface, heating to 200-400 ℃ at a heating rate of 2-20 ℃/min, and preserving the temperature for 30-300 min.
As an improvement of the preparation method of the single-crystal lithium manganate, in S3, the preparation method further comprises coating the surface of the single-crystal lithium manganate.
The second purpose of the invention is: the single-crystal lithium manganate is prepared by adopting the preparation method of the single-crystal lithium manganate in any one of the specifications.
As an improvement of the single-crystal lithium manganate of the present invention, the single-crystal lithium manganate has a spinel-type single-crystal structure and a non-octahedral shape appearance.
The third purpose of the invention is that: the application of the monocrystalline lithium manganate in the lithium ion battery is provided.
Compared with the prior art, the beneficial effects of the invention include but are not limited to:
1) in the invention, the single-crystal lithium manganate is prepared by preparing the manganese single-crystal precursor, and on the one hand, the particle size distribution of the single-crystal lithium manganate is adjusted by controlling the particle size distribution of the manganese single-crystal precursor. On the other hand, in the process of high-temperature solid-phase sintering, the path of lithium ions in a lithium salt molten phase penetrating into the manganese-based single-crystal precursor is optimized through the unique form of the manganese-based single-crystal precursor, so that the generated single-crystal lithium manganate preferentially keeps the appearance of the manganese-based single-crystal precursor, and the appearance of the octahedral form of the single-crystal lithium manganate is inhibited.
2) In the invention, the obtained non-octahedral monocrystal lithium manganate material has a smaller exposed (111) crystal face and a smaller specific surface area, and the purpose of reducing the contact area of Mn elements in lithium manganate and an electrolyte is realized, so that the dissolution probability of Mn ions in a lithium ion battery taking lithium manganate as a positive electrode is reduced, and finally, the cycle performance of the lithium ion battery taking lithium manganate as the positive electrode is greatly improved.
3) In the invention, the monocrystalline lithium manganate has smaller specific surface, the prepared slurry can have higher solid content, and the use amount of a solvent can be reduced; meanwhile, the coated pole piece has larger compacted density (more than 3.0 g/cm)3)。
Drawings
Fig. 1 is an SEM image of a manganese-based single crystal precursor in example 1.
Fig. 2 is an XRD pattern of the manganese-based single crystal precursor in example 1.
FIG. 3 is an SEM photograph of crystalline lithium manganate contained in example 1.
FIG. 4 is an SEM photograph of the lithium manganate of secondary spherical form in comparative example 1.
FIG. 5 is an XRD pattern of single-crystal lithium manganate in example 1.
FIG. 6 is an XRD pattern of secondary spherical lithium manganate in comparative example 1
FIG. 7 is a graph showing the charge and discharge curves of a half cell made of the single crystal lithium manganate in example 1.
FIG. 8 is a graph showing the charge and discharge curves of a half-cell made of the secondary spherical lithium manganate of comparative example 1.
FIG. 9 is a graph showing the cycling at room temperature for a full cell made from the single-crystal lithium manganate of example 1 and the secondary spherical lithium manganate of comparative example 1, respectively.
FIG. 10 is a high temperature (55 ℃ C.) cycling profile for a full cell made from the coated-doped single crystal lithium manganate of example 2.
Detailed Description
The present application is further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
The first aspect of the present application provides a method for preparing single crystal lithium manganate, comprising the following steps:
s1, crystallizing the soluble manganese salt, the alkali liquor, the soluble carbonate and the complexing agent through a complex reaction to obtain a manganese series single crystal precursor with controllable particle size distribution;
s2, mixing the manganese series single crystal precursor with a lithium source to obtain a mixture;
and S3, heating the mixture in air or oxidizing atmosphere to carry out solid-phase sintering reaction to obtain the single crystal lithium manganate with controllable particle size.
In the present invention, the preparation of the manganese-based single crystal precursor in step S1 is critical. The invention mainly adopts liquid phase controllable growth combined with a thermal oxidation method to prepare the manganese series monocrystal precursor. The soluble manganese salt comprises at least one of manganese sulfate, manganese chloride, manganese nitrate, manganese citrate and manganese acetate, the alkali liquor comprises at least one of sodium hydroxide, potassium hydroxide and ammonia water, the soluble carbonate comprises at least one of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate, and the complexing agent comprises at least one of ammonia water, ammonium salt, sodium tartrate, disodium ethylene diamine tetraacetate and citric acid. The soluble manganese salt is dissolved in water to form a solution a. Preparing alkali liquor with a certain concentration as the B liquor. And preparing a certain concentration of soluble carbonate or bicarbonate as the solution C. Complexing agent such as ammonia water or ammonium salt, sodium tartrate, disodium ethylene diamine tetraacetate, citric acid, etc. is used to prepare solution as solution D. Adding a certain amount of crystal nucleus inducer such as aluminum sulfate, zinc sulfate, propylene glycol, ethylene glycol, etc. into the base solution. Inert gas or non-oxidizing gas is introduced in the whole reaction process. A. B, C, D four feeds are fed in a certain proportion. The reaction temperature, the reaction proportion, the reaction time and the like are strictly controlled; under the action of the complexing agent, the crystallization speed is controlled through the complexing effect, the formation of a three-dimensional hexagonal prism-shaped structure can be further ensured, and a product of a columnar crystal is obtained. The manganese hydroxide or carbonate obtained by the precipitation reaction is filtered and washed after aging. And (3) filtering and washing the product, and then carrying out high-temperature treatment on the product to obtain the trimanganese tetroxide or trimanganese trioxide with maintained appearance. In the process of preparing the manganese series single crystal precursor, element doping can be carried out in stages, so that the uniform distribution or gradient distribution of doping elements in the precursor can be controlled.
In the present invention, in S1, a manganese-based single crystal precursor is prepared by a precipitation method, a mixed solvent method, or a hydrothermal method. Preferably, the manganese series single crystal precursor is prepared by a liquid phase method.
In the invention, in S2, directly mixing the manganese series single crystal precursor and the lithium source, and uniformly mixing to obtain a mixture; or adding a solvent into the manganese series single crystal precursor and the lithium source, uniformly mixing and drying to obtain a mixture. Preferably, the manganese series single crystal precursor and the lithium source are directly mixed and then directly and uniformly mixed by a mechanical method and a dry method. Or dissolving the manganese series single crystal precursor and the lithium source in a solvent, mechanically stirring, uniformly mixing and drying; wherein the solvent includes, but is not limited to, ethanol or isopropanol.
In the present invention, in S2, the lithium source includes at least one of lithium oxide, lithium carbonate, lithium nitrate, lithium acetate, and lithium hydroxide.
In the present invention, in S3, the solid-phase sintering reaction includes a primary sintering including the following stepwise heating operation:
1) heating to 450-700 ℃ at the speed of 2-20 ℃/min, and preserving heat for 4-24 h;
2) heating to 750-950 ℃ at the speed of 2-20 ℃/min, and preserving heat for 4-30 h.
In some embodiments, in 1), the elevated temperature heating time is at least 4 hours; in the step 2), the heating time is 4-30 h.
Preferably, 1) raising the temperature to 500 ℃ at the speed of 6 ℃/min, and keeping the temperature for 2 h;
2) heating to 720 ℃ at the speed of 6 ℃/min, and keeping the temperature for 2 h;
3) heating to 820 deg.C at 4 deg.C/min, and maintaining for 12 h.
In the present invention, in S3, the solid-phase sintering reaction further includes cooling the product obtained by the first sintering, grinding or pulverizing the cooled product, and then sintering the product again. The temperature setting of the secondary sintering is basically the same as that of the primary sintering, and the secondary sintering can be adjusted finely according to actual needs. In principle, the temperature does not exceed 950 ℃ and the time does not exceed 24 hours.
In the invention, the impurity type and content in the precursor can be regulated and controlled in the process of preparing the manganese-based single crystal precursor, and the manganese-based single crystal precursor is subjected to homogeneous doping in the process of forming a single crystal by adding the dopant.
In some embodiments, in S1, the method further comprises adding a doping substance to the soluble manganese salt, the alkali solution, the soluble carbonate salt, and the complexing agent;
the doping material comprises at least one of oxide, inorganic salt and organic salt, and contains an element M, wherein the element M is at least one of Li, Ti, Zr, La, Al, Ce, Sr, Pr, Nd, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Sb, Mg, Tm, Bi, Mo, Sn, Zn, V, W, Yb, Lu, B, Y and Sc; the ratio of the total substance amount of the element M in the single-crystal lithium manganate to the substance amount of the manganese element in the manganese-based single-crystal precursor is 1:10, 1:15, 1:20, 1: 25: 1:30, … …, 1:100, 1:200, 1:300, 1:400, 1:500, … …, 1: 1000.
In the invention, the surface of the manganese series single crystal precursor is coated, and the single crystal lithium manganate with doping elements distributed in a gradient manner from the surface to the inside can be formed.
In some embodiments, in S1, further comprising coating the surface of the manganese-based single crystal precursor with a coating substance;
the coating material comprises at least one of oxide, inorganic salt and organic salt, the coating material contains an element M, the element M is at least one of Li, Ti, Zr, La, Al, Ce, Sr, Pr, Nd, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Sb, Mg, Tm, Bi, Mo, Sn, Zn, V, W, Yb, Lu, B, Y and Sc, and the ratio of the total substance amount of the element M in the single-crystal lithium manganate to the substance amount of the manganese element in the surface-coated manganese-based single-crystal precursor is 1:10, 1:15, 1:20, 1: 25: 1:30, … …, 1:100, 1:200, 1:300, 1:400, 1:500, … …, 1: 1000.
In the invention, in S1, after the surface of the manganese-based single crystal precursor is coated with the coating substance, the method further comprises a pretreatment operation, wherein the pretreatment operation comprises drying the manganese-based single crystal precursor coated on the surface, heating to 200-400 ℃ at a heating rate of 2-20 ℃/min, and keeping the temperature for 30-300 min.
In the present invention, in S3, the method further includes surface coating the single-crystal lithium manganate. The coating material may include at least one element selected from Li, Ti, Zr, La, Al, Ce, Sr, Pr, Nd, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Sb, Mg, Tm, Bi, Mo, Sn, Zn, V, W, Yb, Lu, B, Y and Sc. The ratio of the total mass of the coating elements to the mass of the manganese elements is 1: (10-1000). Specifically, the ratio of the total substance amount of the coating elements to the substance amount of the manganese element in the single-crystal lithium manganate is (1: 10, 1:15, 1:20, 1: 25): 1:30, … …, 1:100, 1:200, 1:300, 1:400, 1:500, … …, 1: 1000. The coating process can be carried out after the primary sintering is finished in the step S3, and then secondary sintering is carried out, wherein the secondary sintering temperature can be selected between 450 ℃ and 900 ℃ according to the actual situation, and the time is selected between 2h and 12 h. The coating can also be carried out after the secondary sintering, and after the secondary sintering is finished, heat treatment is needed, wherein the heat treatment temperature is selected between 450 ℃ and 700 ℃, and the time is selected between 2h and 12 h.
The second aspect of the invention provides a single-crystal lithium manganate prepared by the preparation method of the single-crystal lithium manganate in any one of the preceding specifications.
In the invention, the single-crystal lithium manganate has a spinel crystal structure and appearance of non-octahedral shape.
In a third aspect of the invention, there is provided a use of the single-crystal lithium manganate of the preceding description in a lithium ion battery.
Examples
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
Preparation of monocrystalline lithium manganate:
s1: weighing 21.19g of manganese sulfate monohydrate, adding 100g of water for dissolving, transferring to a 250mL volumetric flask after dissolving, fixing the volume, and preparing 250mL of solution containing 0.5mol/L of manganese ions as solution A; taking 250ml of 0.5mol/L diluted ammonia water solution as liquid B; weighing 10.50g of sodium bicarbonate, adding 100g of water for dissolving, transferring to a 250mL volumetric flask after dissolving, fixing the volume, and preparing 250mL of solution containing 0.5mol/L of bicarbonate ions as solution C; 2.42g of sodium tartrate is further weighed and dissolved in 250g of water to be used as a solution D; 10mL of the crystal nucleus inducer glycol was added to 100mL of water as a base solution. Introducing inert gas N in the whole reaction process2Protecting the product from oxidation. Feeding the liquid A, the liquid B, the liquid C and the liquid D at a speed of 0.2ml/min according to a ratio of 1:1:1: 1. Controlling the reaction temperature to be 40 ℃, the stirring speed to be 1000rpm, and the feeding time to be 21 h; under the action of complexing agent sodium tartrate and ammonia water, the crystallization speed is controlled through the complexing effect, the formation of a three-dimensional hexagonal prism-shaped structure can be further ensured, and a product of a columnar crystal is obtained. Precipitating manganese hydroxide carbonate obtained by the reaction, after the reaction is finished, continuously adding ammonia water to adjust the pH value to 9, and aging for 24 h. After aging, suction filtration was performed, and the filter residue was washed with deionized water 3 times. And (3) filtering and washing the product, and treating the product at 850 ℃ for 4h to obtain a manganese sesquioxide type manganese series single crystal precursor A with a maintained shape.
S2: and mixing the manganese single crystal precursor A with lithium carbonate to obtain a mixture B, wherein the using amount of manganese and lithium is 2:1.05 according to the mass ratio, and the mixing mode is that solid powder is directly mechanically stirred and mixed.
S3: putting the mixture B into a sagger, putting the sagger into a muffle furnace, heating to 450 ℃ at the speed of 6 ℃/min, and preserving heat for 2 hours; then heating to 650 ℃ at the speed of 6 ℃/min, and preserving heat for 2 h; finally, heating to 820 ℃ at the speed of 4 ℃/min, and preserving heat for 6 hours to finish primary sintering; cooling to room temperature along with the furnace, grinding the obtained material, putting the ground material into a sagger, putting the sagger into a muffle furnace for secondary sintering, heating to 650 ℃ at the speed of 6 ℃/min, and preserving heat for 2 hours; then heating to 840 ℃ at the speed of 4 ℃/min, and preserving the heat for 6 h; and finally, cooling to room temperature along with the furnace, and grinding and sieving to finally obtain the single crystal lithium manganate with the shape consistent with the precursor. The whole solid phase sintering atmosphere is air atmosphere.
Example 2
Preparation of coated-doped monocrystalline lithium manganate:
s1: weighing 21.19g of manganese sulfate monohydrate, adding 100g of water for dissolving, simultaneously weighing 0.26g of aluminum sulfate octadecahydrate, adding, stirring for dissolving, transferring to a 250mL volumetric flask after dissolving, and fixing the volume to prepare 250mL of 0.5mol/L manganese ion solution containing trace Al as solution A; taking 250ml of 0.5mol/L diluted ammonia water solution as liquid B; weighing 10.50g of sodium bicarbonate, adding 100g of water for dissolving, transferring to a 250mL volumetric flask after dissolving, fixing the volume, and preparing 250mL of solution containing 0.5mol/L of bicarbonate ions as solution C; 2.42g of sodium tartrate was dissolved in 250g of water as solution D. 10mL of the crystal nucleus inducer glycol was added to 100mL of water as a base solution. Introducing inert gas N in the whole reaction process2Protecting the product from oxidation. Feeding the liquid A, the liquid B, the liquid C and the liquid D at a speed of 0.2ml/min according to a ratio of 1:1:1: 1. Controlling the reaction temperature to be 40 ℃, the stirring speed to be 1000rpm, and the feeding time to be 21 h; under the action of complexing agent sodium tartrate and ammonia water, the crystallization speed is controlled through the complexing effect, the formation of a three-dimensional hexagonal prism-shaped structure can be further ensured, and a product of a columnar crystal is obtained. Precipitating to obtain aluminum-doped basic manganese carbonate, continuously adding ammonia water to adjust the pH value to 9 after the reaction is finished, and aging for 24 h. After aging, suction filtration was performed, and the filter residue was washed with deionized water 3 times. And filtering and washing the product, and treating the product at 850 ℃ for 4h to obtain the manganese sesquioxide with maintained shape.
S2: and mixing the manganese single crystal precursor A with lithium carbonate to obtain a mixture B, wherein the using amount of manganese and lithium is 2:1.05 according to the mass ratio, and the mixing mode is that solid powder is directly mechanically stirred and mixed.
S3: putting the mixture B into a sagger, putting the sagger into a muffle furnace, heating to 450 ℃ at the speed of 6 ℃/min, and preserving heat for 2 hours; then heating to 650 ℃ at the speed of 6 ℃/min, and preserving heat for 2 h; finally, heating to 820 ℃ at the speed of 4 ℃/min, and preserving heat for 12h to finish primary sintering; cooling to room temperature along with the furnace, grinding the obtained material, coating aluminum phosphate according to a liquid phase method with the weight of 1%, drying, putting the aluminum phosphate into a sagger, putting the sagger into a muffle furnace for secondary sintering, heating to 650 ℃ at the speed of 6 ℃/min, and preserving heat for 2 hours; then heating to 800 ℃ at the speed of 4 ℃/min, and preserving heat for 6 h; and finally, cooling to room temperature along with the furnace, and grinding and sieving to finally obtain the coated single-crystal lithium manganate with the shape consistent with the precursor. The whole solid phase sintering atmosphere is air atmosphere.
Comparative example 1
Preparation of lithium manganate:
s1: 20g of spherical mangano-manganic oxide is weighed as a manganese precursor.
S2: mixing the precursor with lithium carbonate, wherein the using amount of manganese and lithium is 2:1.05, the mixing mode is that solid powder is directly stirred and mixed mechanically.
S3, placing the mixture into a sagger, placing the sagger into a muffle furnace, heating to 720 ℃ at the speed of 6 ℃/min, and keeping the temperature for 8 hours; and finally, heating to 820 ℃ at the speed of 4 ℃/min, preserving the heat for 8 hours, and cooling to room temperature along with the furnace to obtain the lithium manganate. The whole solid phase sintering atmosphere is air atmosphere.
Performance testing
1) SEM morphology characterization was performed on the materials obtained in example 1 and comparative example 1, as shown in FIGS. 1 and 3-4.
2) XRD tests were performed on the materials obtained in example 1 and comparative example 1, as shown in FIGS. 2 and 5 to 6.
3) The materials obtained in example 1 and comparative example 1 were used as positive electrodes, lithium sheets as counter electrodes, and an electrolyte containing LiPF6The mixed solution of the ethyl carbonate, the ethylene carbonate and the methyl ethyl carbonate is prepared into a button half cell for charge and discharge tests. The test conditions are 2.75V-4.2V and 0.1C charging/discharging at room temperature. The results are shown in FIGS. 7 to 8.
4) The materials obtained in example 1 and comparative example 1 were used as a positive electrode, graphite as a negative electrode, and a mixed solution of ethyl carbonate, ethylene carbonate, and ethyl methyl carbonate containing LiPF6 was used as an electrolyte to prepare a pouch full cell (404050) for cycle performance test. The test conditions are 2.75V-4.2V at room temperature and 1C charge/discharge. The results are shown in FIG. 9.
5) A pouch full cell (404050) was prepared using the material obtained in example 2 as a positive electrode, graphite as a negative electrode, and a mixed solution of ethyl carbonate, ethylene carbonate, and ethyl methyl carbonate containing LiPF6 as an electrolyte, and was subjected to a cycle performance test. The test conditions are 55 ℃, 2.75V-4.2V and 1C charging/discharging. The results are shown in FIG. 10.
Analysis of results
It can be seen from FIG. 1 that the precursor is in a non-octahedral polyhedral form. The structure of the precursor is manganese sesquioxide as can be seen from fig. 2.
With reference to fig. 3 and fig. 1, it can be seen that the lithium manganate prepared by the present invention maintains the morphology of the precursor. Some of the particles have confluent growth between them. No octahedral particles and (111) crystal faces are seen in the whole lithium manganate. In fig. 4, the secondary spherical lithium manganate is formed by aggregating a large number of primary particles.
As can be seen from comparison of FIGS. 5 to 6, the single-crystal lithium manganate prepared by the present invention and the lithium manganate (conventional lithium manganate) prepared by the comparative example 1 are both of cubic spinel type structures.
As can be seen by comparing fig. 7 to 8, the specific discharge capacity (about 108mAh/g) of the half-cell prepared from the single-crystal lithium manganate prepared according to example 1 of the present invention is about 10mAh/g lower than that (about 118mAh/g) of the half-cell prepared from the lithium manganate prepared according to comparative example 1.
As can be seen from FIG. 9, when the single-crystal lithium manganate of example 1 and the lithium manganate of comparative example 1 are respectively assembled into a full cell, the lithium manganate of comparative example 1 has very fast capacity fading, and the capacity retention rate at 50 cycles is already lower than 70%, while the cycle performance of the single-crystal lithium manganate of the present invention is significantly improved, and the capacity retention rate is still higher than 80% after 700 cycles. The reason is that the form of the single-crystal lithium manganate is derived from the form of a precursor, an octahedral appearance structure is avoided, and the contact area between a crystal face (111) with high Mn ion density and an electrolyte is reduced, so that the dissolution probability of Mn ions in a lithium ion battery taking the lithium manganate as a positive electrode is reduced, and the aim of greatly improving the cycle performance is finally achieved.
As can be seen from fig. 10, the full cell fabricated from the single-crystal lithium manganate containing a coating-dopant of example 2 has a better cycle performance at 55 ℃. The capacity retention after 300 weeks of 1C cycling was still greater than 80%. It is known that the cycle performance of lithium manganate at high temperature is poor, which is caused by the fact that the dissolution behavior of Mn element in lithium manganate in electrolyte at high temperature is intensified. According to the invention, doping and coating processes are introduced on the basis of the single-crystal lithium manganate, the structure of the lithium manganate during charging/discharging is further stabilized by the doping effect, the contact of the electrolyte and a solid-liquid interface of the single-crystal lithium manganate is further prevented by the surface coating layer, and the dissolution probability of Mn element in the electrolyte is inhibited. Therefore, the full cell assembled by the coated-doped monocrystalline lithium manganate at the temperature of 55 ℃ has better cycle performance.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (15)
1. A preparation method of single crystal lithium manganate is characterized by comprising the following steps:
s1, crystallizing the soluble manganese salt, the alkali liquor, the soluble carbonate and the complexing agent through a complex reaction to obtain a manganese series single crystal precursor with controllable particle size distribution;
s2, mixing the manganese series single crystal precursor with a lithium source to obtain a mixture;
and S3, heating the mixture in air or oxidizing atmosphere to carry out solid-phase sintering reaction to obtain the single-crystal lithium manganate with controllable particle size.
2. The method for preparing single-crystal lithium manganate as set forth in claim 1, wherein in S1, the soluble manganese salt comprises at least one of manganese sulfate, manganese chloride, manganese nitrate, manganese citrate and manganese acetate, the alkali solution comprises at least one of sodium hydroxide, potassium hydroxide and ammonia water, the soluble carbonate salt comprises at least one of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate, and the complexing agent comprises at least one of ammonia water, ammonium salt, sodium tartrate, disodium ethylenediaminetetraacetate and citric acid.
3. The method for producing single-crystal lithium manganate as set forth in claim 1, wherein the manganese-based single-crystal precursor is produced by a precipitation method, a mixed solvent method or a hydrothermal method in S1.
4. The method for preparing single-crystal lithium manganate as claimed in claim 1, wherein in S2, the manganese-based single-crystal precursor and the lithium source are directly mixed and uniformly mixed to obtain the mixture; or adding a solvent into the manganese series single crystal precursor and the lithium source, uniformly mixing and drying to obtain the mixture.
5. The method for preparing single-crystal lithium manganate as claimed in claim 1, wherein in S2, the lithium source comprises at least one of lithium oxide, lithium carbonate, lithium nitrate, lithium acetate and lithium hydroxide.
6. The method for preparing single-crystal lithium manganate as claimed in claim 1, wherein in S3, the solid-phase sintering reaction comprises a primary sintering, and the primary sintering comprises the following step-wise heating operations:
1) heating to 450-700 ℃ at the speed of 2-20 ℃/min, and preserving heat for 4-24 h;
2) heating to 750-950 ℃ at the speed of 2-20 ℃/min, and preserving heat for 4-30 h.
7. The method for preparing single-crystal lithium manganate as claimed in claim 6, wherein in 1), the heating time at elevated temperature is at least 4 hours; in the step 2), the heating time is 4-30 h.
8. The method for preparing single-crystal lithium manganate as claimed in claim 6, wherein in S3, the solid-phase sintering reaction further comprises cooling the product obtained by the first sintering, grinding or pulverizing the product, and then sintering the product again.
9. The method for preparing single-crystal lithium manganate as claimed in claim 1, wherein in S1, doping materials are added to the soluble manganese salt, the alkali solution, the soluble carbonate and the complexing agent to perform a complexing reaction;
the doping material comprises at least one of oxide, inorganic salt and organic salt, and contains an element M, wherein the element M is at least one of Li, Ti, Zr, La, Al, Ce, Sr, Pr, Nd, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Sb, Mg, Tm, Bi, Mo, Sn, Zn, V, W, Yb, Lu, B, Y and Sc; the ratio of the total substance quantity of the element M in the single-crystal lithium manganate to the substance quantity of the manganese element in the manganese series single-crystal precursor is 1: (10-1000).
10. The method for producing single-crystal lithium manganate as set forth in claim 1, wherein in S1, the method further comprises coating the surface of said manganese-based single-crystal precursor with a coating substance;
the coating material comprises at least one of oxide, inorganic salt and organic salt, the coating material contains an element M, the element M is at least one of Li, Ti, Zr, La, Al, Ce, Sr, Pr, Nd, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Sb, Mg, Tm, Bi, Mo, Sn, Zn, V, W, Yb, Lu, B, Y and Sc, and the ratio of the total substance amount of the element M in the single-crystal lithium manganate to the substance amount of the manganese element in the surface-coated manganese single-crystal precursor is 1: (10-1000).
11. The method for preparing single-crystal lithium manganate as claimed in claim 10, wherein in S1, after coating the surface of the manganese-based single-crystal precursor with a coating substance, the method further comprises a pretreatment operation, wherein the pretreatment operation comprises drying the manganese-based single-crystal precursor coated on the surface, raising the temperature to 200-400 ℃ at a rate of 2-20 ℃/min, and maintaining the temperature for 30-300 min.
12. The method for preparing single-crystal lithium manganate as claimed in claim 1, wherein in S3, further comprising coating the surface of said single-crystal lithium manganate.
13. A single-crystal lithium manganate produced by the method for producing single-crystal lithium manganate according to any one of claims 1 to 12.
14. The single-crystal lithium manganate of claim 13, wherein said single-crystal lithium manganate has a spinel-type single-crystal structure and a non-octahedral-shape appearance.
15. Use of the single-crystal lithium manganate according to claim 13 in a lithium ion battery.
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