CN103606669B - Mix the preparation method of the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium - Google Patents
Mix the preparation method of the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium Download PDFInfo
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- CN103606669B CN103606669B CN201310624430.6A CN201310624430A CN103606669B CN 103606669 B CN103606669 B CN 103606669B CN 201310624430 A CN201310624430 A CN 201310624430A CN 103606669 B CN103606669 B CN 103606669B
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- chromium
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 28
- 239000011029 spinel Substances 0.000 title claims abstract description 28
- 229910052706 scandium Inorganic materials 0.000 title claims abstract description 26
- 239000010406 cathode material Substances 0.000 title claims abstract description 25
- 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 22
- 239000011651 chromium Substances 0.000 title claims abstract description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 16
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 33
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 238000001238 wet grinding Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 13
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 42
- 239000011572 manganese Substances 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 14
- 229910001437 manganese ion Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 229910001430 chromium ion Inorganic materials 0.000 claims description 11
- -1 scandium ion Chemical class 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 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 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical group [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 8
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 229960000359 chromic chloride Drugs 0.000 claims description 6
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- 239000008267 milk Substances 0.000 claims description 5
- 210000004080 milk Anatomy 0.000 claims description 5
- 235000013336 milk Nutrition 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 229940071125 manganese acetate Drugs 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
- 238000003801 milling Methods 0.000 claims description 3
- 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 2
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 claims description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- 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 2
- 235000014872 manganese citrate Nutrition 0.000 claims description 2
- 239000011564 manganese citrate Substances 0.000 claims description 2
- 229940097206 manganese citrate Drugs 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 230000010287 polarization Effects 0.000 abstract description 11
- 230000004087 circulation Effects 0.000 description 20
- 230000008569 process Effects 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 229910015645 LiMn Inorganic materials 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000009768 microwave sintering Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910013553 LiNO Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 229910003174 MnOOH Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WCMHZFHLWGFVCQ-UHFFFAOYSA-N [Ba].[Mn] Chemical compound [Ba].[Mn] WCMHZFHLWGFVCQ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910006290 γ-MnOOH 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to the preparation method of the spinel lithium-rich lithium manganate cathode material of mixing trivalent scandium or chromium, it is characterized in that the mol ratio (0.97≤x≤1.08) according to lithium, manganese, Doped ions?:? (1.05≤y≤1.20)?:? (0.05≤z≤0.17) takes lithium, manganese, the compound of scandium or the compound of chromium respectively.By the compound weighed, add wet grinding media and obtain predecessor 1, predecessor 2 is prepared in drying.Finally use double sintering legal system for the rich lithium manganate cathode material for lithium of doped spinel.Cost of material of the present invention is lower, the electrochemical polarization that doping reduces Lithium-ion embeding and deviates from, and improves heavy-current discharge performance, for industrialization is laid a good foundation.
Description
Technical field
The invention belongs to technical field prepared by battery electrode material, be specifically related to a kind of preparation method that can be used for the rich lithium-spinel manganate cathode material for lithium of lithium battery, lithium ion battery, polymer battery and ultracapacitor.
Technical background
Lithium ion battery has that cell voltage is high, energy density is high, memory-less effect, have extended cycle life, the advantage such as self discharge is low, the performance of performance to lithium ion battery of positive electrode plays a part decision.
The advantages such as it is low that manganese-based anode material has price, green non-pollution are the research emphasis of lithium ion battery.In manganese-based anode material, that studies more has spinelle LiMn
2o
4, stratiform LiMnO
2with layed solid-solution positive electrode.Wherein, stratiform LiMnO
2the less stable of structure when discharge and recharge, studies seldom at present.Spinelle LiMn
2o
4can play a role at 4V and 3V two voltage ranges.For 4V district, with lithium ion in the embedding of the tetrahedron 8a position of spinel structure with deviate from relevant; For 3V district, with lithium ion in the embedding of the octahedra 16c position of spinel structure with deviate from relevant.Lithium ion the tetrahedral site of spinel structure embedding and deviate from the significant change that can not cause sample structure.But, when the discharge and recharge degree of depth is excessive, owing to there is the John-Teller distortion effect of lithium ion, embed in octahedron and deviate from lithium ion sample structure can be caused by cube becoming four directions, discharge capacity rapid decay.Therefore, spinelle LiMn is suppressed
2o
4john-Teller distortion be the key improving its charge-discharge performance.In addition, LiMn
2o
4middle manganese can be dissolved in electrolyte, and during discharge and recharge, the decomposition of electrolyte also may affect the cycle performance of electrode material at higher voltages.
At Li
4mn
5o
12charge and discharge process in, the deintercalation of lithium ion reaction mainly occurs in 3V district, and its theoretical discharge capacity can reach 163mAh/g.With spinelle LiMn
2o
4the 148mAh/g of theoretical capacity compares and significantly improves, and has the possibility becoming the outstanding positive electrode in 3V district.In this material charge and discharge process, structure cell expansion rate is less, has the advantages such as cycle performance is outstanding.But, Li
4mn
5o
12thermal stability bad.Li under high temperature
1+ymn
2-yo
4(y<0.33) easily LiMn is decomposed into
2o
4and Li
2mnO
3[ManthiramA., etal., Ceram.Trans, 1998,92:291-302.], makes Li
4mn
5o
12prepared by very difficult conventional method.Have studied multiple synthetic method, attempted to obtain more desirable preparation method.Comprise solid sintering technology, sol-gal process, hydro thermal method and microwave sintering method etc.
Solid sintering technology is the compound of compound by lithium and manganese, sintering preparation under aerobic or oxygen free condition.Takada etc. [TakadaT., J.SolidStateChem., 1997,130:74-80.] are by lithium salts (LiNO
3, Li
2cO
3, Li (CH
3) and manganese compound (MnCO COO)
3, Mn (NO
3)
2, Mn
2o
3and MnO
2) mixing, obtain Li 500 DEG C of-800 DEG C of temperature ranges
4mn
5o
12.[KangS.H., etal., the Electrochem.Solid-StateLett. such as Kang, 2000,3 (12): 536-639.] and [FumioS., the etal. such as Fumio, J.PowerSources, 1997,68 (2): 609-612.] first dry LiOHH
2o and Mn (Ac)
24H
2the mixed solution of O, then in 500 DEG C of obtained Li [Li of sintering
ymn
2-y] O
4.Li [the Li that they prepare
ymn
2-y] O
4the discharge capacity of sample in 3V district is 115-126mAh/g.In oxygen atmosphere, Takada etc. [TakadaT., etal., J.PowerSources, 1997,68:613-617.] find, 500 DEG C of sintering CH
3cOOLi and Mn (NO
3)
2the product that obtains of fused mass be 135mAh/g in the discharge capacity of the 1st circulation.When Shin etc. [ShinY., etal., Electrochim.Acta, 2003,48 (24): 3583 – 3592.] think that sintering temperature is lower than 500 DEG C, Mn
3+amount increase discharge capacity is increased.[KajiyamaA., etal., J.JapanSoc.Powder & PowderMetallurgy, 2000,47 (11): 1139-1143 such as Kajiyama; NakamuraT.etal., SolidStateIonics, 1999,25:167-168.] by LiOHH
2o and γ-Mn
2o
3mixing, they find, the Li prepared in oxygen atmosphere
4mn
5o
12chemical property better than what prepare at air atmosphere.Xu Meihuas etc. [XuM.H., etal., J.Phys.Chem, 2010,114 (39): 16143 – 16147.] and Tian etc. [TianY., etal., Chem.Commun., 2007:2072 – 2074.] are by MnSO
4add LiNO
3and NaNO
3fuse salt in, can nanometer Li be obtained 470 DEG C of-480 DEG C of temperature ranges
4mn
5o
12.Nano wire Li prepared by Tian etc. [TianY., etal., Chem.Commun., 2007:2072 – 2074.]
4mn
5o
12154.3mAh/g and 140mAh/g is respectively in (under 0.2C multiplying power electric current) the 1st circulation and the 30th discharge capacity circulated.Thackeray etc. [ThackerayM.M, etal., J.SolidStateChem., 1996,125:274-277.; MichaelM., etal., AmericanCeram.Soc.Bull, 1999,82 (12): 3347-3354.] by LiOHH
2o and γ-MnO
2mixing, 600 DEG C of sintering can obtain Li
4mn
5o
12.Yang etc. [YangX., etal., J.SolidStateChem., 2000,10:1903-1909.] are by γ-MnO
2or β-MnO
2or the LiNO of barium manganese ore or acid birnessite and melting
3mixing, can obtain Li at 400 DEG C
1.33mn
1.67o
4.Liu Cong [Liu Cong. the synthesis and property [D] of lithium ion battery mangaic acid lithium cathode material. Guangdong: South China Normal University, 2009.] first by LiOHH
2o and electrolysis MnO
2mix in absolute ethyl alcohol, in 450 DEG C of sintering in air atmosphere, then ball milling obtains sample in ethanol.The most high discharge capacity of the sample that they prepare is 161.1mAh/g, and the discharge capacity of the 30th circulation is higher than 120mAh/g.
Kim etc. [KimJ., etal., J.Electrochem.Soc, 1998,145 (4): 53-55.] are at LiOH and Mn (CH
3cOO)
2mixed solution in add Li
2o
2, first obtained Li
xmn
yo
znH
2o, then obtain Li through filtration, washing, drying and solid-phase sintering
4mn
5o
12.They find, the initial discharge capacity of the sample of 500 DEG C of preparations is 153mAh/g, and the capacity attenuation rate of 40 circulations is 2%.Manthiram etc. [ManthiramA., etal., J.Chem.Mater, 1998,10 (10): 2895-2909.] research shows, in LiOH solution, and Li
2o
2initial oxidation [Mn (H
2o)
6]
2+, then through 400 DEG C of sintering, the Li of preparation
4mn
5o
12the 1st circulation discharge capacity be 160mAh/g.
In order to improve solid sintering technology process conditions, double sintering method is used to preparation process.Li righteous armies etc. [Li righteous army etc., non-ferrous metal, 2007,59 (3): 25-29.] are by LiOH, Mn (C
2o
4)
2and H
2c
2o
4mixture be placed in air atmosphere, prepare micron Li at 350 DEG C and 500 DEG C of sintering respectively
4mn
5o
12.The sample of preparation is 151mAh/g in the discharge capacity of the 1st circulation.[GaoJ., etal., Appl.Phys.Lett., 1995,66 (19): 2487-2489. such as Gao; GaoJ., etal., J.Electrochem.Soc., 1996,143 (6): 1783-1788.] adopt two step heatings to prepare spinelle Li
1+xmn
2-xo
4x(0<x≤0.2).Robertson etc. [RobertsonA.D., etal., J.PowerSources, 2001,97-97:332-335.] are at Mn (CH
3cOO)
24H
2li is mixed in O solution
2cO
3, dry acquisition precursor.Li has been prepared respectively at 250 DEG C and 300-395 DEG C of sintering
4mn
5o
12.Sample the 1st circulates and the discharge capacity of the 50th circulation is respectively 175mAh/g and 120mAh/g.Wang etc. [WangG.X., etal., J.PowerSources, 1998,74 (2): 198-201.] have synthesized Li at 380 DEG C
4mn
5o
12.Xia [XiaY.Y., etal., J.PowerSources, 1996,63 (1): 97-102.] etc., by injection method, obtain sample at 260 DEG C of direct sinterings.Under C/3 electric current, the discharge capacity first of this sample is 80mAh/g.
More than research shows, solid sintering technology prepares Li
4mn
5o
12need at pure O
2or carry out in air atmosphere.The shortcoming of this method comprise the composition of synthetic product and particle size distribution difference large, the capacity attenuation rate of sample charge and discharge cycles is high, and heavy-current discharge performance is not good, and high temperature cyclic performance is more undesirable.
In order to improve the uniformity of sample, reduce the granularity of sample particle, sol-gal process is used to prepare Li
4mn
5o
12[HaoY.J., etal., J.SolidStateElectrochem., 2009,13:905 – 912; Meng Lili etc., inorganic chemicals industry, 2009,46 (5): 37-39; ChuH.Y., etal., J.Appl.Electrochem, 2009,39:2007-2013.].Open [a meeting feelings etc., battery, 2004,34 (3): 176-177.] such as meeting feelings by LiOH2H
2o, Mn (CH
3cOO)
24H
2the mixture of O and citric acid is respectively at 300 DEG C and 500 DEG C of obtained micron spinelle Li of sintering
4mn
5o
12.
In order to improve the uniformity of sample, reduce the granularity of sample particle, reduce sintering temperature, hydro thermal method is also used to preparation process.Zhang [ZhangY.C., etal., Mater.Res.Bull., 2002,37 (8): 1411-1417.; Zhang Yongcai. hydro-thermal and solvent-thermal process metastable phase functional material are studied [D]. Beijing: Beijing University of Technology, 2003.; ZhangY.C., etal., J.SolidStateIonics, 2003,158 (1): 113-117.] etc. first by H
2o
2, LiOH and Mn (NO
3)
2the obtained fibrous presoma Li of mixed solution reaction
xmn
yo
znH
2o, then react obtained nanometer Li with LiOH solution low-temperature hydrothermal
4mn
5o
12.Generation superfine [generation is superfine. a kind of synthesis Li
4mn
5o
12method [P] .CN201010033605.2 of sub-micrometer rod, applying date 2010.01.04.] by MnSO
4h
2o, KMnO
4first obtain sub-micron MnOOH with the mixture of softex kw 140 DEG C-180 DEG C temperature range hydro-thermal reactions, then be mixed into LiOHH
2o, finally in 500 DEG C of-900 DEG C of obtained Li
4mn
5o
12.Sun Shuying etc. [Sun Shuying etc., inorganic material Leader, 2010,25 (6): 626-630.] by hydro-thermal reaction, by MnSO
4h
2o and (NH
4)
2s
2o
8obtained nanometer β-MnO
2, be mixed into LiNO
3after again by the obtained Li of low-temperature solid-phase method reaction
4mn
5o
12.
Because microwave sintering method has sintering velocity soon, the advantages such as sintering process is easy, the method that microwave sintering method or solid-phase sintering-microwave sintering combine is used to synthesize LiMn
2o
4.Ahniyaz etc. [AhniyazA., etal., J.Eng.Mater.Technol., 2004,264-268:133-136.] are by γ-MnOOH, LiOH and H
2o
2mixture synthesized LiMn by microwave sintering method
2o
4.Tong Qingsong seminar is with LiOH and Mn (CH
3cOO)
2for raw material [Lin Suying etc., Fujian chemical industry, 2004,2:1-4.; Tong Qingsong etc., electrochemistry, 2005,11 (4): 435-439.] or with LiOH and MnC
2o
4for raw material [Tong Qingsong etc., Fujian Normal University's journal, 2006,22 (1): 60-63.], with disodium EDTA (EDTA) and citric acid for complexing agent, adopt microwave-solid phase double sintering method, prepared spinelle Li at 380 DEG C
3.22na
0.569mn
5.78o
12sample or Li
4mn
5o
12positive electrode.Research shows, at 4.5-2.5V voltage range, and the Li of preparation
3.22na
0.569mn
5.78o
12sample is 132mAh/g in the discharge capacity of the 1st circulation, and the capacity attenuation rate of 100 circulations is 6.8%.Through 4 months deposit, this sample initial discharge capacity was 122mAh/g, and the capacity attenuation rate of 100 circulations is 17.4%.
Guo Junming etc. [Guo Junming etc., functional material, 2006,37:485-488.] for raw material, make fuel with urea with lithium nitrate and manganese nitrate (or with lithium acetate and manganese acetate), adopt liquid-phase combustion legal system to obtain Li
4mn
5o
12.They find, the Li of acetate system synthesis
4mn
5o
12the height that synthesizes compared with nitrate system of thing phase purity.Kim etc. [KimH.U., etal., Phys.Scr, 2010,139:1-6.] find, with by liquid phase synthesis approach in 400 DEG C sintering samples with micro-Mn
2o
3.Under 1C multiplying power electric current, the discharge capacity that sample the 1st circulates is 44.2mAh/g.Zhao etc. [ZhaoY., etal., Electrochem.Solid-StateLett., 2010,14:1509 – 1513.] adopt water-in-oil microemulsion method to synthesize nano spinel Li
4mn
5o
12.
Due to spinelle Li prepared by said method
4mn
5o
12in charge and discharge process, structural stability is not high, there is the problems such as discharge performance under low temperature discharge, high temperature circulation and big current is poor.Adopt Surface coating, added high polymer, Doped anions or cationic method carried out modification.
In order to improve Li
4mn
5o
12cycle performance, Liu Cong [Liu Cong, the synthesis and property of lithium ion battery mangaic acid lithium cathode material, South China Normal University's academic dissertation, 2009.] polyvinylpyrrolidonesolution solution is mixed with 450 DEG C of predecessors prepared, respectively through oxygen atmosphere process at hydro-thermal K cryogenic treatment, vacuum treatment, drying and 100 DEG C, obtained Li
4mn
5o
12.Research shows, under 0.5C multiplying power electric current, sample is respectively 137mAh/g and 126mAh/g in the discharge capacity of the 1st circulation and the 50th circulation.
In order to improve spinelle Li further
4mn
5o
12performance, adopted cation and anion doped method to improve the performance of sample.Zhang etc. [ZhangD.B., etal., J.PowerSources, 1998,76:81-90.] are with CrO
2.65, Li (OH) H
2o and MnO
2for raw material, respectively at 300 DEG C and 450 DEG C of sintering in oxygen atmosphere, prepare Li
4cr
ymn
5-yo
12(y=0,0.3,0.9,1.5,2.1).Research shows, at 0.25mA/cm
2under electric current, Li
4cr
1.5mn
3.5o
12sample is respectively 170mAh/g and 152Ah/g in the discharge capacity of the 1st circulation and the 100th circulation.Robertson etc. [RobertsonA.D., etal., J.PowerSources, 2001,97-97:332-335.] are at Mn (CH
3cOO)
24H
2o and Co (CH
3cOO)
24H
2first Li is added in O mixed solution
2cO
3, prepare precursor, respectively at 250 DEG C and 430-440 DEG C of sintering after drying, obtained Li
4-xmn
5-2xco
3xo
12sample.This sample is respectively 175mAh/g and 120mAh/g in the discharge capacity of the 1st circulation and the 50th circulation.With Li
4mn
5o
12compare, in charge and discharge cycles process, Li
4-xmn
5-2xco
3xo
12structure more stable.Wherein, Li
3.75mn
4.5co
0.075o
12the 1st circulation discharge capacity be 150mAh/g, 50 circulation capacity attenuation rates close to 0%.Choi etc. [ChoiW., etal., SolidStateIonics, 2007,178:1541-1545.] are by LiOH, LiF and Mn (OH)
2mixing, prepares Li respectively at 500 DEG C and 600 DEG C of double sinterings in air atmosphere
4mn
5o
12 ηf
η(0≤η≤0.2).Wherein, under 0.2C multiplying power electric current, the Li of 500 DEG C of preparations
4mn
5o
11.85f
0.1the 1st circulation discharge capacity be 158mAh/g.After at 25 DEG C and 60 DEG C, discharge and recharge 50 circulates, the capacity attenuation rate of this sample is respectively 2.9% and 3.9%, illustrates that the initial discharge capacity of mixing fluorine sample under high temperature and low temperature and cycle performance are improved.
Though said method can the chemical property of improvement sample in various degree, but, due to spinelle Li
4mn
5o
12the stability of structure is good not, transfers poor electrical performance at low temperature and heavy-current discharge condition, and at high temperature cycle performance can obviously decay.For this reason, the present invention by mix scandium or chromium method promote Li
4mn
5o
12the actual oxidation state of middle manganese, the oxidation state delaying manganese in discharge process, lower than the process of+3.5, reduces the impact of Jahn-Teller distortion on structural stability.Known following parameter, H
f298Sc-O=674kJmol
1, H
f298Cr-O=427kJmol
1, H
f298OCr-O=531kJmol
1, H
f298Mn-O=402kJmol
1, r
sc-O=74.5pm (Sc oxidation state is+3, and its ligancy is 6), r
cr-O=61.5pm (Cr oxidation state is+3, and its ligancy is 6), r
mn-O=39pm (Mn oxidation state is+4, and its ligancy is 4), r
mn-O=53pm (Mn oxidation state is+4, and its ligancy is 6) [JohnA.Dean, HandbookofChemistry (15
thedition)].From above parameter, Sc-O key and Cr-O key more much bigger than the intensity of Mn-O key, the ionic radius of scandium ion and chromium ion is large compared with the radius of manganese ion, and therefore, replacing part manganese ion with a small amount of scandium ion or chromium ion can not produce large impact to doping spline structure.Due to scandium ion or chromium ion slightly larger compared with manganese ion original in spinel structure, the cell configuration of doping sample is expanded to some extent, and lithium ion embeds and deviates to be more prone in doped samples, reduce Lithium-ion embeding and deviate from time electrochemical polarization.In addition, due to the scandium ion of doping or chromium ion, in doping sample, to manifest oxidation state be+3, improves the relative oxidation state of manganese ion, be delayed the process that Jahn-Teller distortion occurs manganese ion, the cycle performance of the doping sample of preparation is significantly improved.
Summary of the invention
For avoiding the deficiencies in the prior art, the present invention adopts the method for doping scandium ion or chromium ion to improve spinelle Li
4mn
5o
12the stability of structure, electrochemical polarization when reducing Lithium-ion embeding and deviate from.The technical scheme adopted for realizing object of the present invention is:
Step 1: be compound, the compound of manganese, the compound of doping that x:y:z takes lithium respectively according to the mol ratio of lithium ion, manganese ion, Doped ions.The span of described x, y and z meets following relational expression simultaneously: 1.20≤y+z≤1.25,0.97≤x≤1.08,1.05≤y≤1.20,0.05≤z≤0.17.
Step 2: the compound of the compound of lithium step 1 taken, the compound of manganese and doping, adds 1 times of wet grinding media to 15 times of volumes of mixed total solid capacity, mix 3 hours ~ 15 hours with wet milling device wet-milling, obtained predecessor 1.By predecessor 2 dry to predecessor 1 constant pressure and dry, vacuumize or the preparation of spray-dired method.Predecessor 2 is placed in air, oxygen-enriched air or pure oxygen atmosphere, adopts double sintering legal system for spinel lithium-rich lithium manganate cathode material.
Described double sintering method is carried out as follows: the predecessor 2 of drying is placed in air, oxygen-enriched air or pure oxygen atmosphere, 3 hours ~ 15 hours are sintered in arbitrary temperature of 150 DEG C ~ 300 DEG C of temperature ranges, then be heated to arbitrary temperature of 400 DEG C ~ 600 DEG C of temperature ranges by last sintering temperature according to the firing rate of 1 DEG C/min ~ 30 DEG C/min, temperature is kept to sinter 3 hours ~ 24 hours, preparation spinel lithium-rich lithium manganate cathode material.
Described Doped ions is scandium ion or chromium ion.
The compound of described doping is the compound of scandium or the compound of chromium.
The compound of described scandium is Sc
2o
3, scandium nitrate, ScCl
3, Sc (OH)
3, Sc
2(SO
4)
3or Sc
2(C
2o
4)
3.
The compound of described chromium is Cr
2o
3, chromium hydroxide, potassium chromium sulfate, chromium sulfate or chromium trichloride.
The compound of described lithium is lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride or lithium citrate.
The compound of described manganese is manganese carbonate, basic carbonate manganese, manganous hydroxide, manganese acetate, manganese nitrate, manganese chloride or manganese citrate.
Described constant pressure and dry is arbitrary temperature predecessor 1 being placed in 140 DEG C ~ 280 DEG C of temperature ranges, dry at 1 atmosphere pressure, prepares predecessor 2.Described vacuumize is arbitrary temperature predecessor being placed in 80 DEG C ~ 280 DEG C of temperature ranges, dry under arbitrary pressure of 10Pa ~ 10132Pa pressure range, prepares predecessor 2.Described spray drying process is arbitrary temperature predecessor 1 being placed in 130 DEG C ~ 280 DEG C of temperature ranges, carries out drying, prepare predecessor 2 with spray dryer.
Described wet grinding media is deionized water, distilled water, ethanol, acetone, methyl alcohol or formaldehyde.
Described oxygen-enriched air is that oxygen volume content is greater than 21% and is less than the oxygen-enriched air between 100%.
Described wet milling device comprises general milling machine, super ball mill or wet milk.
Compared with other inventive method, cost of material of the present invention is lower, and the electrochemical polarization reducing Lithium-ion embeding He deviate from, improves heavy-current discharge performance, for industrialization is laid a good foundation.
Accompanying drawing explanation
Fig. 1 is the 1st discharge curve circulated of the sample prepared by the embodiment of the present invention 1.
Fig. 2 is the XRD diffraction pattern of the JCPDS card of sample prepared by the embodiment of the present invention 1 and correspondence.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed.Embodiment is only supplement further of the present invention and illustrate, instead of the restriction to invention.
Embodiment 1
Be that 0.99:1.20:0.05 takes lithium hydroxide, manganese nitrate and Sc (OH) respectively according to the mol ratio of lithium ion, manganese ion, scandium ion
3.
By the lithium hydroxide, manganese nitrate and the Sc (OH) that take
3mixing, adds the ethanol of 10 times of volumes of total solid capacity, mixes 12 hours with super ball mill wet-milling, obtained predecessor 1.Predecessor 1 is placed in 180 DEG C and the drying of 100Pa vacuum under pressure, prepares predecessor 2.Predecessor 2 is placed in the oxygen-enriched air atmosphere of oxygen volume content 63%, sinters 12 hours at 197 DEG C, be then heated to 530 DEG C according to the firing rate of 5 DEG C/min by 197 DEG C, keep temperature to sinter 20 hours, preparation spinel lithium-rich lithium manganate cathode material.
Compared with other inventive method, cost of material of the present invention is lower, and the electrochemical polarization reducing Lithium-ion embeding He deviate from, improves heavy-current discharge performance, for industrialization is laid a good foundation.
Embodiment 2
Be that 1.02:1.08:0.17 takes lithium carbonate, basic carbonate manganese and Cr respectively according to the mol ratio of lithium ion, manganese ion, chromium ion
2o
3.
By the lithium carbonate, basic carbonate manganese and the Cr that take
2o
3mixing, adds the deionized water of 15 times of volumes of total solid capacity, mixes 12 hours with super ball mill wet-milling, obtained predecessor 1.At predecessor 1 is placed in 130 DEG C, dry with spray dryer, prepare predecessor 2.Predecessor 2 is placed in the oxygen-enriched air atmosphere of oxygen volume content 99%, sinters 3 hours at 290 DEG C, be then heated to 495 DEG C according to the firing rate of 1 DEG C/min by 290 DEG C, keep temperature to sinter 19 hours, preparation spinel lithium-rich lithium manganate cathode material.
Compared with other inventive method, cost of material of the present invention is lower, and the electrochemical polarization reducing Lithium-ion embeding He deviate from, improves heavy-current discharge performance, for industrialization is laid a good foundation.
Embodiment 3
Be that 0.97:1.05:0.15 takes lithium acetate, manganese chloride and scandium nitrate respectively according to the mol ratio of lithium ion, manganese ion, scandium ion.
By lithium acetate, manganese chloride and the scandium nitrate mixing taken, add the acetone of 1 times of volume of total solid capacity, mix 3 hours with the wet-milling of general milling machine, obtained predecessor 1.Predecessor 1 is placed in 80 DEG C and the drying of 10Pa vacuum under pressure, prepares predecessor 2.Predecessor 2 is placed in the oxygen-enriched air atmosphere of oxygen volume content 22%, sinters 3 hours at 150 DEG C, be then heated to 400 DEG C according to the firing rate of 1 DEG C/min by 150 DEG C, keep temperature to sinter 3 hours, preparation spinel lithium-rich lithium manganate cathode material.
Compared with other inventive method, cost of material of the present invention is lower, and the electrochemical polarization reducing Lithium-ion embeding He deviate from, improves heavy-current discharge performance, for industrialization is laid a good foundation.
Embodiment 4
Be that 1.08:1.20:0.05 takes lithium chloride, manganese carbonate and Sc respectively according to the mol ratio of lithium ion, manganese ion, scandium ion
2(C
2o
4)
3.
By the lithium chloride, manganese carbonate and the Sc that take
2(C
2o
4)
3mixing, adds the distilled water of 12 times of volumes of total solid capacity, mixes 15 hours with wet milk wet-milling, obtained predecessor 1.Predecessor 1 is placed in the vacuum under pressure drying of 280 DEG C and 10132Pa, prepares predecessor 2.Predecessor 2 is placed in the oxygen-enriched air atmosphere of oxygen volume content 99%, sinters 15 hours at 300 DEG C, be then heated to 600 DEG C according to the firing rate of 30 DEG C/min by 300 DEG C, keep temperature to sinter 24 hours, preparation spinel lithium-rich lithium manganate cathode material.
Compared with other inventive method, cost of material of the present invention is lower, and the electrochemical polarization reducing Lithium-ion embeding He deviate from, improves heavy-current discharge performance, for industrialization is laid a good foundation.
Embodiment 5
Be that 1.08:1.08:0.12 takes lithium carbonate, manganous hydroxide and chromium sulfate respectively according to the mol ratio of lithium ion, manganese ion, chromium ion.
The lithium carbonate taken, manganous hydroxide and chromium sulfate are mixed, adds the methyl alcohol of 1 times of volume of total solid capacity, mix 15 hours with super ball mill wet-milling, obtained predecessor 1.At predecessor 1 is placed in 280 DEG C, carry out drying with spray dryer, prepare predecessor 2.Predecessor 2 is placed in air atmosphere, sinters 15 hours at 300 DEG C, be then heated to 400 DEG C according to the firing rate of 2 DEG C/min by 300 DEG C, keep temperature to sinter 24 hours, preparation spinel lithium-rich lithium manganate cathode material.
Compared with other inventive method, cost of material of the present invention is lower, and the electrochemical polarization reducing Lithium-ion embeding He deviate from, improves heavy-current discharge performance, for industrialization is laid a good foundation.
Embodiment 6
Be that 1:1.11:0.11 takes lithium hydroxide, manganese nitrate, chromium trichloride respectively according to the mol ratio of lithium ion, manganese ion, chromium ion.
The lithium hydroxide taken, manganese nitrate, chromium trichloride are mixed, adds the methyl alcohol of 5 times of volumes of total solid capacity, mix 12 hours with wet milk wet-milling, obtained predecessor 1.Carry out drying under predecessor 1 being placed in 280 DEG C and 1 atmospheric pressure, prepare predecessor 2.Predecessor 2 is placed in pure oxygen atmosphere, sinters 10 hours at 275 DEG C, be then heated to 539 DEG C according to the firing rate of 1 DEG C/min by 275 DEG C, keep temperature to sinter 3 hours, preparation spinel lithium-rich lithium manganate cathode material.
Compared with other inventive method, cost of material of the present invention is lower, and electrochemical polarization when reducing Lithium-ion embeding and deviate from, improves heavy-current discharge performance, for industrialization is laid a good foundation.
Embodiment 7
Be that 1:1.11:0.11 takes lithium hydroxide, manganese nitrate, chromium trichloride respectively according to the mol ratio of lithium ion, manganese ion, chromium ion.
The lithium hydroxide taken, manganese nitrate, chromium trichloride are mixed, adds the methyl alcohol of 10 times of volumes of total solid capacity, mix 15 hours with wet milk wet-milling, obtained predecessor 1.Carry out drying under predecessor 1 being placed in 140 DEG C and 1 atmospheric pressure, prepare predecessor 2.Predecessor 2 is placed in air atmosphere, sinters 10 hours at 285 DEG C, be then heated to 539 DEG C according to the firing rate of 1 DEG C/min by 285 DEG C, keep temperature to sinter 10 hours, preparation spinel lithium-rich lithium manganate cathode material.
Compared with other inventive method, cost of material of the present invention is lower, and electrochemical polarization when reducing Lithium-ion embeding and deviate from, improves heavy-current discharge performance, for industrialization is laid a good foundation.
Claims (7)
1. mix the preparation method of the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium, it is characterized in that preparation process is made up of following steps:
Step 1: the compound, the compound of manganese, the compound of doping that take lithium according to the mol ratio x:y:z of lithium ion, manganese ion, Doped ions respectively; The span of described x, y and z meets following relational expression simultaneously: 1.20≤y+z≤1.25,0.97≤x≤1.08,1.05≤y≤1.20,0.05≤z≤0.17; Described Doped ions is scandium ion or chromium ion; The compound of described doping is the compound of scandium or the compound of chromium;
Step 2: the compound of the compound of lithium step 1 taken, the compound of manganese and doping, adds 1 times of wet grinding media to 15 times of volumes of mixed total solid capacity, mix 3 hours ~ 15 hours with wet milling device wet-milling, obtained predecessor 1; By predecessor 2 dry to predecessor 1 constant pressure and dry, vacuumize or the preparation of spray-dired method; Predecessor 2 is placed in air, oxygen-enriched air or pure oxygen atmosphere, adopts double sintering legal system for spinel lithium-rich lithium manganate cathode material; The compound of described manganese is manganese carbonate, basic carbonate manganese, manganous hydroxide, manganese acetate, manganese nitrate, manganese chloride or manganese citrate;
Described double sintering method is carried out as follows: the predecessor 2 of drying is placed in air, oxygen-enriched air or pure oxygen atmosphere, 3 hours ~ 15 hours are sintered in arbitrary temperature of 150 DEG C ~ 300 DEG C of temperature ranges, then be heated to arbitrary temperature of 400 DEG C ~ 600 DEG C of temperature ranges by last sintering temperature according to the firing rate of 1 DEG C/min ~ 30 DEG C/min, temperature is kept to sinter 3 hours ~ 24 hours, preparation spinel lithium-rich lithium manganate cathode material.
2. the preparation method mixing the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium according to claim 1, is characterized in that the compound of described lithium is lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride or lithium citrate.
3. the preparation method mixing the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium according to claim 1, is characterized in that the compound of described scandium is Sc
2o
3, scandium nitrate, ScCl
3, Sc (OH)
3, Sc
2(SO
4)
3or Sc
2(C
2o
4)
3; The compound of described chromium is Cr
2o
3, chromium hydroxide, potassium chromium sulfate, chromium sulfate or chromium trichloride.
4. the preparation method mixing the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium according to claim 1, it is characterized in that described constant pressure and dry is arbitrary temperature predecessor 1 being placed in 140 DEG C ~ 280 DEG C of temperature ranges, dry at 1 atmosphere pressure, prepare predecessor 2; Described vacuumize is arbitrary temperature predecessor 1 being placed in 80 DEG C ~ 280 DEG C of temperature ranges, dry under arbitrary pressure of 10Pa ~ 10132Pa pressure range, prepares predecessor 2; Described spraying dry is arbitrary temperature predecessor 1 being placed in 130 DEG C ~ 280 DEG C of temperature ranges, carries out drying, prepare predecessor 2 with spray dryer.
5. the preparation method mixing the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium according to claim 1, is characterized in that described wet grinding media is deionized water, distilled water, ethanol, acetone, methyl alcohol or formaldehyde.
6. the preparation method mixing the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium according to claim 1, is characterized in that described oxygen-enriched air is that oxygen volume content is greater than 21% and is less than the air between 100%.
7. the preparation method mixing the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium according to claim 1, is characterized in that described wet milling device is general milling machine, super ball mill or wet milk.
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| CN1556552A (en) * | 2004-01-10 | 2004-12-22 | 昆明理工大学 | Manufacturing method of lithium ion battery positive electrode material |
| CN1773749A (en) * | 2004-11-11 | 2006-05-17 | 中国科学技术大学 | Method for producing Sc (III) doped spinel type lithium manganate cell positive electrode material |
| CN101719546A (en) * | 2009-11-26 | 2010-06-02 | 上海大学 | Method for preparing lithium ion battery anode material doped with nanometer oxide |
| CN102544442A (en) * | 2010-12-30 | 2012-07-04 | 北京当升材料科技股份有限公司 | Preparation method of lithium manganate precursor |
| CN102683669A (en) * | 2011-12-19 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Cathode material of lithium ion battery and preparation method of cathode material |
| CN102881891A (en) * | 2012-10-15 | 2013-01-16 | 福建师范大学 | Method for preparing trivalent ion-doped lithium-rich solid solution cathode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556552A (en) * | 2004-01-10 | 2004-12-22 | 昆明理工大学 | Manufacturing method of lithium ion battery positive electrode material |
| CN1773749A (en) * | 2004-11-11 | 2006-05-17 | 中国科学技术大学 | Method for producing Sc (III) doped spinel type lithium manganate cell positive electrode material |
| CN101719546A (en) * | 2009-11-26 | 2010-06-02 | 上海大学 | Method for preparing lithium ion battery anode material doped with nanometer oxide |
| CN102544442A (en) * | 2010-12-30 | 2012-07-04 | 北京当升材料科技股份有限公司 | Preparation method of lithium manganate precursor |
| CN102683669A (en) * | 2011-12-19 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Cathode material of lithium ion battery and preparation method of cathode material |
| CN102881891A (en) * | 2012-10-15 | 2013-01-16 | 福建师范大学 | Method for preparing trivalent ion-doped lithium-rich solid solution cathode material |
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