CN103594704A - Preparation method for tetravalent titanium ion-doped spinel lithium-rich lithium manganate positive electrode material - Google Patents
Preparation method for tetravalent titanium ion-doped spinel lithium-rich lithium manganate positive electrode material Download PDFInfo
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- CN103594704A CN103594704A CN201310624619.5A CN201310624619A CN103594704A CN 103594704 A CN103594704 A CN 103594704A CN 201310624619 A CN201310624619 A CN 201310624619A CN 103594704 A CN103594704 A CN 103594704A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000010936 titanium Substances 0.000 title claims abstract description 33
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- 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
- 229910052596 spinel Inorganic materials 0.000 title abstract description 10
- 239000011029 spinel Substances 0.000 title abstract description 10
- 239000007774 positive electrode material Substances 0.000 title abstract 3
- 238000005245 sintering Methods 0.000 claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 238000001238 wet grinding Methods 0.000 claims abstract description 17
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 39
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 36
- 239000011572 manganese Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 239000010406 cathode material Substances 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 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
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 239000008267 milk Substances 0.000 claims description 4
- 210000004080 milk Anatomy 0.000 claims description 4
- 235000013336 milk Nutrition 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical group CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 claims description 4
- SOBXOQKKUVQETK-UHFFFAOYSA-H titanium(3+);trisulfate Chemical compound [Ti+3].[Ti+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SOBXOQKKUVQETK-UHFFFAOYSA-H 0.000 claims description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 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 description 3
- 239000007921 spray Substances 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
- MSYNCHLYGJCFFY-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;titanium(4+) Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O MSYNCHLYGJCFFY-UHFFFAOYSA-B 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 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
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 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
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000002243 precursor Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 4
- -1 titanium ions Chemical class 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 230000004087 circulation Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 10
- 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
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000009768 microwave sintering Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910013553 LiNO Inorganic materials 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007772 electrode material Substances 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
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 229910018663 Mn O Inorganic materials 0.000 description 2
- 229910003176 Mn-O Inorganic materials 0.000 description 2
- 229910003077 Ti−O 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 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
- 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
- 229910009343 Li1.33 Mn1.67 O4 Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 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
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 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
- 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
- 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
- 239000002904 solvent Substances 0.000 description 1
- 238000002910 structure generation Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 229910006290 γ-MnOOH Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—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
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- 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 invention relates to a preparation method for a tetravalent titanium ion-doped spinel lithium-rich lithium manganate positive electrode material. The preparation method is characterized by comprising the following steps: weighing corresponding compounds according to a mol ratio of lithium ions to manganese ions to titanium ions of (0.95 <= x <= 1.06): (1.05 <= y <= 1.25): (0.05 <= z <= 0.25); mixing the weighed compounds and adding a wet grinding medium to prepare a precursor 1; drying the precursor 1 to prepare a precursor 2; and subjecting the precursor 2 to two-stage sintering so as to prepare the tetravalent titanium ion-doped spinel lithium-rich lithium manganate positive electrode material. The invention has the following advantages: cost for raw material is low; high current discharging performance of a sample is improved through addition of titanium; and a good foundation is laid for industrialization.
Description
Technical field
The invention belongs to technical field prepared by battery electrode material, be specifically related to a kind of preparation method who 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 positive electrode plays a part decision to the performance of lithium ion battery.
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, studying morely has spinelle LiMn
2o
4, stratiform LiMnO
2with layed solid-solution positive electrode.Wherein, stratiform LiMnO
2the less stable of structure when discharging and recharging, studies seldom at present.Spinelle LiMn
2o
4can play a role at 4V and two voltage ranges of 3V.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 is in the embedding of the tetrahedral site of spinel structure and deviate from the significant change that can not cause sample structure.Yet, when discharging and recharging the degree of depth when excessive, owing to there being the John-Teller distortion effect of lithium ion, in octahedron, embedding and deviate from lithium ion and can cause sample structure by cube becoming four directions, discharge capacity decays fast.Therefore, suppress spinelle LiMn
2o
4john-Teller distortion be the key of improving its charge-discharge performance.In addition LiMn,
2o
4middle manganese can be dissolved in electrolyte, and while discharging and recharging under high voltage, the decomposition of electrolyte also may affect the cycle performance of electrode material.
At Li
4mn
5o
12charge and discharge process in, the de-embedding reaction of lithium ion mainly occurs in 3V district, its theoretical discharge capacity can reach 163mAh/g.With spinelle LiMn
2o
4the 148mAh/g of theoretical capacity compares obvious raising, has the possibility that becomes 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.Yet, Li
4mn
5o
12thermal stability bad.Li under high temperature
1+ymn
2-yo
4(y < 0.33) is easily decomposed into LiMn
2o
4and Li
2mnO
3[Manthiram A., et al., Ceram.Trans, 1998,92:291-302.], makes Li
4mn
5o
12be difficult to prepare with conventional method.After deliberation multiple synthetic method, attempt 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 by the compound of the compound of lithium and manganese, sintering preparation under aerobic or oxygen free condition.Takada etc. [Takada T., J. Solid State Chem., 1997,130:74-80.] are by lithium salts (LiNO
3, Li
2cO
3, Li (CH
3and manganese compound (MnCO COO))
3, Mn (NO
3)
2, Mn
2o
3and MnO
2) mix, 500 ℃ of-800 ℃ of temperature ranges, make Li
4mn
5o
12.[Kang S. H., et al., the Electrochem. Solid-State Lett. such as Kang, 2000,3 (12): 536-639.] and [Fumio S., the et al. such as Fumio, J. Power Sources, 1997,68 (2): 609-612.] first dry LiOHH
2o and Mn (Ac)
24H
2the mixed solution of O, then make Li[Li in 500 ℃ of sintering
ymn
2-y] O
4.The Li[Li that they prepare
ymn
2-y] O
4the discharge capacity in sample 3V district is 115-126mAh/g.In oxygen atmosphere, Takada etc. [Takada T., et al., J. Power Sources, 1997,68:613-617.] find, 500 ℃ of sintering CH
3cOOLi and Mn (NO
3)
2the product that makes of fused mass in the discharge capacity of the 1st circulation, be 135mAh/g.When Shin etc. [Shin Y., et al., Electrochim. Acta, 2003,48 (24): 3583 – 3592.] think that sintering temperature is lower than 500 ℃, Mn
3+amount increase discharge capacity is increased.[Kajiyama A., et al., J. Japan Soc. Powder & Powder Metallurgy, 2000,47 (11): 1139-1143 such as Kajiyama; Nakamura T. et al., Solid State Ionics, 1999,25:167-168.] by LiOHH
2o and γ-Mn
2o
3mix, they find, the Li preparing in oxygen atmosphere
4mn
5o
12chemical property better than what prepare at air atmosphere.Xu Meihuas etc. [Xu M. H., et al., J. Phys. Chem, 2010,114 (39): 16143 – 16147.] and Tian etc. [Tian Y., et al., Chem. Commun., 2007:2072 – 2074.] are by MnSO
4add LiNO
3and NaNO
3fuse salt in, 470 ℃ of-480 ℃ of temperature ranges, can make nanometer Li
4mn
5o
12.Nano wire Li prepared by Tian etc. [Tian Y., et al., Chem. Commun., 2007:2072 – 2074.]
4mn
5o
12discharge capacity in (under 0.2C multiplying power electric current) the 1st circulation and the 30th circulation is respectively 154.3mAh/g and 140mAh/g.Thackeray etc. [Thackeray M. M,, et al., J. Solid State Chem., 1996,125:274-277.; Michael M., et al., American Ceram. Soc. Bull, 1999,82 (12): 3347-3354.] by LiOHH
2o and γ-MnO
2mix, 600 ℃ of sintering can make Li
4mn
5o
12.Yang etc. [Yang X., et al., J. Solid State Chem., 2000,10:1903-1909.] are by γ-MnO
2or β-MnO
2or the LiNO of barium manganese ore or acid birnessite and melting
3mix, at 400 ℃, can make Li
1.33mn
1.67o
4.Liu Cong [Liu Cong. the synthetic and performance [D] of lithium ion battery LiMn2O4 cathode material. Guangdong: South China Normal University, 2009.] first by LiOHH
2o and electrolysis MnO
2in absolute ethyl alcohol, mix, in air atmosphere, in 450 ℃ of sintering, then ball milling obtains sample in ethanol.The 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. [Kim J., et al., J. Electrochem. Soc, 1998,145 (4): 53-55.] are at LiOH and Mn (CH
3cOO)
2mixed solution in add Li
2o
2, first make Li
xmn
yo
znH
2o, then through filtration, washs, is dried and solid-phase sintering makes Li
4mn
5o
12.They find, the initial discharge capacity of the sample of 500 ℃ of preparations is 153mAh/g, and the capacity attenuation rates of 40 circulations are 2%.Manthiram etc. [Manthiram A., et al., J. Chem. Mater, 1998,10 (10): 2895-2909.] study and show, in LiOH solution, and Li
2o
2initial oxidation [Mn (H
2o)
6]
2+, then through 400 ℃ of sintering, the Li of preparation
4mn
5o
12discharge capacity in the 1st circulation is 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, respectively at 350 ℃ and 500 ℃ of sintering preparation micron Li
4mn
5o
12.The sample of preparation is 151mAh/g in the discharge capacity of the 1st circulation.[Gao J., et al., Appl. Phys. Lett., 1995,66 (19): 2487-2489. such as Gao; Gao J., et al., 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. [Robertson A. D., et al., J. Power Sources, 2001,97-97:332-335.] are at Mn (CH
3cOO)
24H
2in O solution, sneak into Li
2cO
3, the dry precursor that obtains.Respectively at 250 ℃, prepared Li with 300-395 ℃ of sintering
4mn
5o
12.The discharge capacity of sample the 1st circulation and the 50th circulation is respectively 175mAh/g and 120mAh/g.Wang etc. [Wang G. X., et al., J. Power Sources, 1998,74 (2): 198-201.] have synthesized Li at 380 ℃
4mn
5o
12.Xia[Xia Y. Y., et al., J. Power Sources, 1996,63 (1): 97-102.] etc. by injection method, at 260 ℃ of direct sinterings, make sample.Under C/3 electric current, the discharge capacity first of this sample is 80mAh/g.
More than research shows, solid sintering technology is prepared Li
4mn
5o
12need be 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, heavy-current discharge performance is not good, 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[Hao Y. J., et al., J. Solid State Electrochem., 2009,13:905 – 912; Meng Lili etc., inorganic chemicals industry, 2009,46 (5): 37-39; Chu H. Y., et al., 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 makes a micron spinelle Li at 300 ℃ and 500 ℃ of sintering respectively
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[Zhang Y. C., et al., Mater. Res. Bull., 2002,37 (8): 1411-1417.; Zhang Yongcai. the synthetic metastable phase functional material research of hydro-thermal and solvent heat [D]. Beijing: Beijing University of Technology, 2003.; Zhang Y. C., et al., J. Solid State Ionics, 2003,158 (1): 113-117.] etc. first by H
2o
2, LiOH and Mn (NO
3)
2mixed solution reaction make fibrous presoma Li
xmn
yo
znH
2o, then react and make nanometer Li with LiOH solution low-temperature hydrothermal
4mn
5o
12.Generation superfine [generation is superfine. a kind of synthetic Li
4mn
5o
12the method of sub-micrometer rod [P]. CN 201010033605.2, applying date 2010.01.04.] by MnSO
4h
2o, KMnO
4140 ℃ of-180 ℃ of temperature range hydro-thermal reactions, first make sub-micron MnOOH with the mixture of softex kw, then sneak into LiOHH
2o, finally makes Li in 500 ℃-900 ℃
4mn
5o
12.Sun Shuying etc. [Sun Shuying etc., inorganic material Leader, 2010,25 (6): 626-630.] are by hydro-thermal reaction, by MnSO
4h
2o and (NH
4)
2s
2o
8make nanometer β-MnO
2, sneak into LiNO
3after by low-temperature solid-phase method, react and make Li again
4mn
5o
12.
The advantages such as to have sintering velocity fast due to microwave sintering method, and sintering process is easy, the method that microwave sintering method or solid-phase sintering-microwave sintering combine is used to synthetic LiMn
2o
4.Ahniyaz etc. [Ahniyaz A., et al., J. Eng. Mater. Technol., 2004,264-268:133-136.] are by γ-MnOOH, LiOH and H
2o
2mixture by microwave sintering method, synthesized LiMn
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 Deng， Fujian Normal University journal, 2006,22 (1): 60-63.], take disodium EDTA (EDTA) and citric acid is complexing agent, adopts microwave-solid phase double sintering method, at 380 ℃, has prepared spinelle Li
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.] as raw material, make fuel with urea with lithium nitrate and manganese nitrate (or take lithium acetate and manganese acetate), adopt liquid-phase combustion legal system to obtain Li
4mn
5o
12.They find, the Li that acetate system is synthetic
4mn
5o
12the phase purity height synthetic compared with nitrate system.Kim etc. [Kim H. U., et al., Phys. Scr, 2010,139:1-6.] find, with by liquid phase route of synthesis in the sample of 400 ℃ of sintering with micro-Mn
2o
3.Under 1C multiplying power electric current, the discharge capacity of sample the 1st circulation is 44.2mAh/g.Zhao etc. [Zhao Y., et al., Electrochem. Solid-State Lett., 2010,14:1509 – 1513.] adopt water-in-oil microemulsion method to synthesize nano spinel Li
4mn
5o
12.
The spinelle Li preparing due to said method
4mn
5o
12in charge and discharge process, structural stability is not high, has under low temperature discharge, high temperature circulation and large electric current the problems such as discharge performance is poor.Adopted surface to be coated, to add high polymer, doping anion or cationic method to carry out modification.
In order to improve Li
4mn
5o
12cycle performance, Liu Cong [Liu Cong, synthetic and the performance of lithium ion battery LiMn2O4 cathode material, South China Normal University's academic dissertation, 2009.] polyvinylpyrrolidonesolution solution is mixed with the predecessor of 450 ℃ of preparations, respectively through hydro-thermal K cryogenic treatment, vacuum treatment, dry and 100 ℃ at oxygen atmosphere process, make Li
4mn
5o
12.Research shows, under 0.5C multiplying power electric current, sample is respectively 137mAh/g and 126mAh/g in the 1st circulation and the 50th discharge capacity circulating.
In order further to improve spinelle Li
4mn
5o
12performance, adopted cation and anion doped method to improve the performance of sample.Zhang etc. [Zhang D. B., et al., J. Power Sources, 1998,76:81-90.] are with CrO
2.65, Li (OH) H
2o and MnO
2for raw material, in oxygen atmosphere, respectively at 300 ℃ and 450 ℃ of sintering, prepared 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. [Robertson A. D., et al., J. Power Sources, 2001,97-97:332-335.] are at Mn (CH
3cOO)
24H
2o and Co (CH
3cOO)
24H
2in O mixed solution, first add Li
2cO
3, prepare precursor, after being dried, respectively at 250 ℃ and 430-440 ℃ of sintering, make 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
12discharge capacity in the 1st circulation is 150mAh/g, and the capacity attenuation rate of 50 circulations approaches 0%.Choi etc. [Choi W., et al., Solid State Ionics, 2007,178:1541-1545.] are by LiOH, LiF and Mn (OH)
2mix, in air atmosphere, respectively at 500 ℃ and 600 ℃ of double sinterings, prepare Li
4mn
5o
12 ηf
η(0≤η≤0.2).Wherein, under 0.2C multiplying power electric current, the Li of 500 ℃ of preparations
4mn
5o
11.85f
0.1discharge capacity in the 1st circulation is 158mAh/g.At 25 ℃ and 60 ℃, discharge and recharge after 50 circulations, the capacity attenuation rate of this sample is respectively 2.9% and 3.9%, illustrates that initial discharge capacity and the cycle performance of under high temperature and low temperature, mixing fluorine sample are improved.
Though above-mentioned preparation method can improve the chemical property of sample, but, the spinelle Li preparing at present
4mn
5o
12in charge and discharge process, the stability of structure is good not, under low temperature and heavy-current discharge condition, shows poor discharge performance, the at high temperature obvious decay of cycle performance etc.For this reason, the present invention improves Li by mixing titanium method
4mn
5o
12chemical property.Known following parameter, H
f 298 Ti-O=662 kJ mol
1, H
f 298 Mn-O=402 kJ mol
1, r
ti-O=68pm (oxidation state of Ti is+4, and its ligancy is 6), r
mn-O=39pm (oxidation state of Mn is+4, and its ligancy is 4), r
mn-O=53pm (oxidation state of Mn is+4, and its ligancy is 6) [John A. Dean, Handbook of Chemistry(15
thedition)].From above parameter, Ti-O key is more much bigger than the intensity of Mn-O key, and titanium ion is larger than the radius of manganese ion, therefore, with a small amount of titanium ion, replaces the large impact of structure generation that part manganese ion can be on the sample of preparation.Because the oxidation state of titanium in doped samples is+4, on the not significantly impact of the actual oxidation state of manganese in sample.Titanium ion is to the strong active force of having of oxonium ion in spinel structure, and in charge and discharge process, the structural stability of sample improves.In mixing titanium sample, the radius of the manganese ion that the radius ratio of titanium ion is partly replaced is larger, the embedding of lithium ion and deviating from while being conducive to discharge and recharge, and the heavy-current discharge performance of mixing titanium sample is significantly improved.
Summary of the invention
For avoiding the deficiencies in the prior art, the present invention adopts Doped with Titanium to improve spinelle Li
4mn
5o
12the stability of structure.In mixing titanium sample, because titanium ion has strong active force to the oxonium ion of spinel structure, improved the stability of sample structure.The radius of the manganese ion that the radius ratio of titanium ion is partly replaced is large, and the embedding of lithium ion and deviating from while being conducive to discharge and recharge improves the heavy-current discharge performance of mixing titanium sample, for realizing the technical scheme that object of the present invention adopts, is:
Step 1: be that x: y: z takes respectively the compound of lithium, the compound of the compound of manganese, titanium according to the mol ratio of lithium ion, manganese ion, titanium ion.The span of described x, y and z meets following calculating formula simultaneously: 1.20≤y+z≤1.30,0.95≤x≤1.06,1.05≤y≤1.25,0.05≤z≤0.25.
Step 2: the compound of the compound of the lithium that step 1 is taken, the compound of manganese and titanium, add 1 times of wet grinding media to 15 times of volumes of mixed total solid capacity, with the wet-milling of wet-milling equipment, mix 3 hours～15 hours, make predecessor 1.Predecessor 1 use constant pressure and dry, vacuumize or spray-dired method are prepared to dry predecessor 2.Predecessor 2 is placed in to air, oxygen-enriched air or pure oxygen atmosphere, adopts double sintering legal system for the rich lithium manganate cathode material for lithium of spinelle.
Described double sintering method is carried out as follows: dry predecessor 2 is placed in to air, oxygen-enriched air or pure oxygen atmosphere, arbitrary temperature sintering of 150 ℃～300 ℃ of temperature ranges 3 hours～15 hours, the firing rate of following according to 1 ℃/min～30 ℃/min is heated to arbitrary temperature of 400 ℃～600 ℃ of temperature ranges by last sintering temperature, keep temperature sintering 3 hours～24 hours, prepare the rich lithium manganate cathode material for lithium of spinelle.
The compound of described lithium is lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride or lithium citrate.
The compound of described titanium is titanium monoxide, titanium dioxide, Titanium Nitrate, titanium tetrachloride, titanium trichloride, butyl titanate, titanium sesquisulfate or Titanium Citrate.
The compound of described manganese is manganese oxide, manganese carbonate, basic carbonate manganese, manganous hydroxide, manganese acetate, manganese nitrate, manganese chloride or manganese citrate.
Described constant pressure and dry is the arbitrary temperature 130 ℃～280 ℃ of temperature ranges by predecessor 1, under 1 atmospheric pressure, is dried, and prepares predecessor 2.Described vacuumize is the arbitrary temperature 80 ℃～280 ℃ of temperature ranges by predecessor 1, under arbitrary pressure of 10Pa～10132Pa pressure range, is dried, and prepares predecessor 2.Described spray drying process is the arbitrary temperature 140 ℃～280 ℃ of temperature ranges by predecessor 1, and it is dry that employing spray dryer carries out, and prepares predecessor 2.
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 be less than the oxygen-enriched air between 100%.
Described wet-milling equipment comprises general milling machine, super ball mill or wet milk.
Compare with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, and preparation process is simple, consuming time few, and the electrode material of preparation forms evenly, and the present invention adopts doped titanium method to improve spinelle Li
4mn
5o
12structural stability, be conducive to improve the heavy-current discharge performance mix titanium sample, for industrialization is laid a good foundation.
Accompanying drawing explanation
Fig. 1 is the discharge capacity of the prepared sample of the embodiment of the present invention 1 and the graph of relation of period.
Fig. 2 is the XRD diffraction pattern of the JCPDS card of the prepared sample of the embodiment of the present invention 1 and correspondence.
Embodiment
Below in conjunction with embodiment, the present invention is further described.Embodiment further supplements and explanation of the present invention, rather than the restriction to invention.
Embodiment 1
According to the mol ratio of lithium ion, manganese ion, titanium ion, be respectively to take lithium hydroxide, manganous hydroxide, titanium trichloride at 1: 1.15: 0.10.
The lithium hydroxide taking, manganous hydroxide, titanium trichloride are mixed, add the ethanol of 10 times of volumes of total solid capacity, with super ball mill wet-milling, mix 10 hours, make predecessor 1.By predecessor 1 vacuumize under 170 ℃ and 1005 Pa, prepare predecessor 2.Predecessor 2 is placed in to the oxygen-enriched air atmosphere of oxygen volume content 55%, 195 ℃ of sintering 10 hours, then according to the firing rate of 6 ℃/min, by 195 ℃, is heated to 560 ℃, keep temperature sintering 20 hours, prepare the rich lithium manganate cathode material for lithium of spinelle.
Compare with other inventive method, cost of material of the present invention is lower, mixes the spinelle Li that titanium has improved preparation
4mn
5o
12the stability of structure, be conducive to improve the heavy-current discharge performance of mixing titanium sample of preparation, for industrialization is laid a good foundation.
According to the mol ratio of lithium ion, manganese ion, titanium ion, be 0.95:1.05: 0.15 takes respectively lithium carbonate, manganese acetate, titanium dioxide.
The lithium carbonate taking, manganese acetate, titanium dioxide are mixed, add the deionized water of 1 times of volume of total solid capacity, with super ball mill wet-milling, mix 3 hours, make predecessor 1.Predecessor 1 is dried with 10Pa vacuum under pressure at 80 ℃, prepares predecessor 2.Predecessor 2 is placed in to the oxygen-enriched air atmosphere of oxygen volume content 22%, 150 ℃ of sintering 3 hours, then according to the firing rate of 1 ℃/min, by 150 ℃, is heated to 400 ℃, keep temperature sintering 3 hours, prepare the rich lithium manganate cathode material for lithium of spinelle.
Compare with other inventive method, cost of material of the present invention is lower, mixes the spinelle Li that titanium has improved preparation
4mn
5o
12structural stability, improve the heavy-current discharge performance mix titanium sample, for industrialization is laid a good foundation.
Embodiment 3
According to the mol ratio of lithium ion, manganese ion, titanium ion, be respectively to take lithium chloride, manganese nitrate, titanium monoxide at 1.06: 1.25: 0.05.
The lithium chloride taking, manganese nitrate, titanium monoxide are mixed, add the methyl alcohol of 15 times of volumes of total solid capacity, with the wet-milling of general milling machine, mix 15 hours, make predecessor 1.Predecessor 1 is dry at 280 ℃ and 10132 Pa vacuum under pressure, prepare predecessor 2.Predecessor 2 is placed in to the oxygen-enriched air atmosphere of oxygen volume content 99%, 300 ℃ of sintering 15 hours, then according to the firing rate of 30 ℃/min, by 300 ℃, is heated to 600 ℃, keep temperature sintering 24 hours, prepare the rich lithium manganate cathode material for lithium of spinelle.
Compare with other inventive method, cost of material of the present invention is lower, mixes the spinelle Li that titanium has improved preparation
4mn
5o
12structural stability, improve the heavy-current discharge performance mix titanium sample, for industrialization is laid a good foundation.
Embodiment 4
According to the mol ratio of lithium ion, manganese ion, titanium ion, be respectively to take lithium nitrate, manganese oxide, Titanium Nitrate at 0.95: 1.25: 0.05.
The lithium nitrate taking, manganese oxide, Titanium Nitrate are mixed, add the deionized water of 15 times of volumes of total solid capacity, with the wet-milling of general milling machine, mix 15 hours, make predecessor 1.Predecessor 1 is placed at 140 ℃, with spray dryer, is dried, prepare predecessor 2.Predecessor 2 is placed in to pure oxygen atmosphere, 295 ℃ of sintering 3 hours, then according to the firing rate of 2 ℃/min, by 295 ℃, is heated to 590 ℃, keep temperature sintering 5 hours, prepare the rich lithium manganate cathode material for lithium of spinelle.
Compare with other inventive method, cost of material of the present invention is lower, mixes titanium and has improved spinelle Li
4mn
5o
12structural stability, be also conducive to improve the heavy-current discharge performance mix titanium sample, for industrialization is laid a good foundation.
Embodiment 5
According to the mol ratio of lithium ion, manganese ion, titanium ion, be respectively to take lithium carbonate, manganese acetate, titanium sesquisulfate at 1.06: 1.05: 0.25.
The lithium carbonate taking, manganese acetate, titanium sesquisulfate are mixed, add the distilled water of 2 times of volumes of total solid capacity, with wet milk wet-milling, mix 15 hours, make predecessor 1.By predecessor 1 constant pressure and dry under 130 ℃ and 1 atmospheric pressure, prepare predecessor 2.Predecessor 2 is placed in to air atmosphere, 190 ℃ of sintering 3 hours, then according to the firing rate of 5 ℃/min, by 190 ℃, is heated to 400 ℃, keep temperature sintering 3 hours, prepare the rich lithium manganate cathode material for lithium of spinelle.
Compare with other inventive method, cost of material of the present invention is lower, mixes titanium and has improved spinelle Li
4mn
5o
12structural stability, improved the heavy-current discharge performance of mixing titanium sample, for industrialization is laid a good foundation.
Embodiment 6
According to the mol ratio of lithium ion, manganese ion, titanium ion, be respectively to take lithium hydroxide, manganous hydroxide, titanium dioxide at 1: 1.15: 0.12.
The lithium hydroxide taking, manganous hydroxide, titanium dioxide are mixed, add the distilled water of 8 times of volumes of total solid capacity, with wet milk wet-milling, mix 9 hours, make predecessor 1.By predecessor 1 constant pressure and dry under 280 ℃ and 1 atmospheric pressure, prepare predecessor 2.Predecessor 2 is placed in to air atmosphere, 270 ℃ of sintering 15 hours, then according to the firing rate of 1 ℃/min, by 270 ℃, is heated to 400 ℃, keep temperature sintering 24 hours, prepare the rich lithium manganate cathode material for lithium of spinelle.
Compare with other inventive method, cost of material of the present invention is lower, mixes the spinelle Li that titanium has improved preparation
4mn
5o
12structural stability, improve the heavy-current discharge performance mix titanium sample, for industrialization is laid a good foundation.
Claims (8)
1. the preparation method of the rich lithium manganate cathode material for lithium of spinelle of doping titanic ion, is characterized in that preparation process is comprised of following steps:
Step 1: be that x: y: z takes respectively the compound of lithium, the compound of the compound of manganese, titanium according to the mol ratio of lithium ion, manganese ion, titanium ion; The span of described x, y and z meets following relational expression simultaneously: 1.20≤y+z≤1.30,0.95≤x≤1.06,1.05≤y≤1.25,0.05≤z≤0.25;
Step 2: the compound of the compound of the lithium that step 1 is taken, the compound of manganese and titanium, add 1 times of wet grinding media to 15 times of volumes of mixed total solid capacity, with the wet-milling of wet-milling equipment, mix 3 hours～15 hours, make predecessor 1; Predecessor 1 use constant pressure and dry, vacuumize or spray-dired method are prepared to dry predecessor 2; Predecessor 2 is placed in to air, oxygen-enriched air or pure oxygen atmosphere, adopts double sintering legal system for the rich lithium manganate cathode material for lithium of spinelle;
Described double sintering method is carried out as follows: dry predecessor 2 is placed in to air, oxygen-enriched air or pure oxygen atmosphere, arbitrary temperature sintering of 150 ℃～300 ℃ of temperature ranges 3 hours～15 hours, the firing rate of following according to 1 ℃/min～30 ℃/min is heated to arbitrary temperature of 400 ℃～600 ℃ of temperature ranges by last sintering temperature, keep temperature sintering 3 hours～24 hours, prepare the rich lithium manganate cathode material for lithium of spinelle.
2. the preparation method of the rich lithium manganate cathode material for lithium of the spinelle of doping titanic ion 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 of the rich lithium manganate cathode material for lithium of the spinelle of doping titanic ion according to claim 1, is characterized in that the compound of described titanium is titanium monoxide, titanium dioxide, Titanium Nitrate, titanium tetrachloride, titanium trichloride, butyl titanate, titanium sesquisulfate or Titanium Citrate.
4. the preparation method of the rich lithium manganate cathode material for lithium of the spinelle of doping titanic ion according to claim 1, is characterized in that the compound of described manganese is manganese oxide, manganese carbonate, basic carbonate manganese, manganous hydroxide, manganese acetate, manganese nitrate, manganese chloride or manganese citrate.
5. the preparation method of the rich lithium manganate cathode material for lithium of the spinelle of doping titanic ion according to claim 1, it is characterized in that described constant pressure and dry is the arbitrary temperature 130 ℃～280 ℃ of temperature ranges by predecessor 1, under 1 atmospheric pressure, be dried, prepare predecessor 2; Described vacuumize is the arbitrary temperature 80 ℃～280 ℃ of temperature ranges by predecessor 1, under arbitrary pressure of 10Pa～10132Pa pressure range, is dried, and prepares predecessor 2; Described spray drying process is the arbitrary temperature 140 ℃～280 ℃ of temperature ranges by predecessor 1, and it is dry that employing spray dryer carries out, and prepares predecessor 2.
6. the preparation method of the rich lithium manganate cathode material for lithium of the spinelle of doping titanic ion according to claim 1, is characterized in that described wet grinding media is deionized water, distilled water, ethanol, acetone, methyl alcohol or formaldehyde.
7. the preparation method of the rich lithium manganate cathode material for lithium of the spinelle of doping titanic ion according to claim 1, is characterized in that described oxygen-enriched air is that oxygen volume content is greater than 21% and be less than the air between 100%.
8. the preparation method of the rich lithium manganate cathode material for lithium of the spinelle of doping titanic ion according to claim 1, is characterized in that described wet-milling equipment is general milling machine, super ball mill or wet milk.
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| CN105958057A (en) * | 2016-07-06 | 2016-09-21 | 福建师范大学 | Method for improving tetravalent cation doped spinel lithium-rich lithium manganate by using acidic salt |
| CN110921720A (en) * | 2019-12-03 | 2020-03-27 | 江南大学 | High-voltage lithium ion battery positive electrode material and preparation method thereof |
| CN111883769A (en) * | 2020-06-30 | 2020-11-03 | 国网浙江省电力有限公司湖州供电公司 | Preparation method of flame-retardant energy storage negative electrode material and lithium ion battery |
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| CN110921720A (en) * | 2019-12-03 | 2020-03-27 | 江南大学 | High-voltage lithium ion battery positive electrode material and preparation method thereof |
| CN110921720B (en) * | 2019-12-03 | 2022-02-15 | 江南大学 | High-voltage lithium ion battery positive electrode material and preparation method thereof |
| CN111883769A (en) * | 2020-06-30 | 2020-11-03 | 国网浙江省电力有限公司湖州供电公司 | Preparation method of flame-retardant energy storage negative electrode material and lithium ion battery |
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