CN106298257A - A kind of high-performance titanium-containing oxide, Preparation Method And The Use - Google Patents
A kind of high-performance titanium-containing oxide, Preparation Method And The Use Download PDFInfo
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- CN106298257A CN106298257A CN201610714858.3A CN201610714858A CN106298257A CN 106298257 A CN106298257 A CN 106298257A CN 201610714858 A CN201610714858 A CN 201610714858A CN 106298257 A CN106298257 A CN 106298257A
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- China
- Prior art keywords
- titanium
- conductive agent
- containing oxide
- gas
- agent presoma
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 239000010936 titanium Substances 0.000 title claims abstract description 92
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 76
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 13
- 150000004767 nitrides Chemical class 0.000 claims abstract description 4
- 239000006258 conductive agent Substances 0.000 claims description 70
- 239000002253 acid Substances 0.000 claims description 62
- 239000007789 gas Substances 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 47
- 239000012159 carrier gas Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 238000005229 chemical vapour deposition Methods 0.000 claims description 30
- 230000006872 improvement Effects 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 20
- 230000008021 deposition Effects 0.000 claims description 20
- 229910052756 noble gas Inorganic materials 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 230000020477 pH reduction Effects 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkoxide compound Chemical class 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 229910000085 borane Inorganic materials 0.000 claims description 7
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052743 krypton Inorganic materials 0.000 claims description 6
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052754 neon Inorganic materials 0.000 claims description 6
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229910003918 SiC1+x Inorganic materials 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- PNCDAXYMWHXGON-UHFFFAOYSA-N ethanol;niobium Chemical compound [Nb].CCO.CCO.CCO.CCO.CCO PNCDAXYMWHXGON-UHFFFAOYSA-N 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 2
- NTQGILPNLZZOJH-UHFFFAOYSA-N disilicon Chemical compound [Si]#[Si] NTQGILPNLZZOJH-UHFFFAOYSA-N 0.000 claims description 2
- JVOQKOIQWNPOMI-UHFFFAOYSA-N ethanol;tantalum Chemical compound [Ta].CCO JVOQKOIQWNPOMI-UHFFFAOYSA-N 0.000 claims description 2
- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 2
- LVNAMAOHFNPWJB-UHFFFAOYSA-N methanol;tantalum Chemical compound [Ta].OC.OC.OC.OC.OC LVNAMAOHFNPWJB-UHFFFAOYSA-N 0.000 claims description 2
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims description 2
- ZGYICYBLPGRURT-UHFFFAOYSA-N tri(propan-2-yl)silicon Chemical compound CC(C)[Si](C(C)C)C(C)C ZGYICYBLPGRURT-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- 235000011054 acetic acid Nutrition 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 239000007792 gaseous phase Substances 0.000 claims 1
- 238000007740 vapor deposition Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 150000003608 titanium Chemical class 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 description 13
- 230000008901 benefit Effects 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000012808 vapor phase Substances 0.000 description 4
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Metallurgy (AREA)
- Battery Electrode And Active Subsutance (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The present invention relates to a kind of high-performance titanium-containing oxide, Preparation Method And The Use.The titanium-containing oxide of the present invention includes lithium titanate particle and is coated on the conductive network film on lithium titanate particle surface, and the chemical composition of conductive network film therein is any one or the combination of at least two in boride, nitride or carbide.In the titanium-containing oxide of the present invention, fine and close conductive network film is closely combined in the surface of lithium titanate particle, and the electric conductivity of this titanium-containing oxide is preferable, and tap density is higher, and the order of magnitude of conductivity is 10‑3～10‑2S/cm, tap density is 1.3～2.0g/cm3, battery volume energy height, the internal resistance made using this titanium-containing oxide as negative pole are little, and high rate capability is excellent, and under the high magnification of 10C and 20C, charge specific capacity is respectively at more than 168mAh/g and more than 160mAh/g.
Description
Technical field
The invention belongs to battery capacitor field of material technology, relate to a kind of titanium-containing oxide, Preparation Method And The Use, especially
It relates to a kind of high-performance titanium-containing oxide, its preparation method and is used as the purposes of negative material.
Background technology
Lithium-ion mixture super capacitor is a kind of a kind of energy storage device between ultracapacitor and secondary cell,
Close at Aero-Space, track traffic, electric automobile and the demand high-energy-density such as electronic information and instrument and meter, high power
The field of degree storage has huge application potential, and electrode material is as one of key factor determining capacitor performance, is
The emphasis of research at present.
There is the lithium titanate (Li of spinel structure4Ti5O12) send out hardly due to its lattice paprmeter during embedding de-lithium
Changing, is referred to as " zero strain " material, and its theoretical intercalation potential is 1.55V (vs Li/Li+), theoretical specific capacity is
175mAh/g, has that safety is high, charge-discharge performance is good, cycle performance is excellent and the advantage such as charging/discharging voltage platform stable.Titanium
Acid lithium, as cell negative electrode material, has obtained preliminary application at present in terms of lithium-ion-power cell.But, due to metatitanic acid
Electric conductivity and the high rate performance of lithium are on the low side, it is impossible to be widely used in the Power capacitor industry of high power density demand, it is therefore desirable to
Material is modified, to meet its application at Power capacitor industry.
CN 104852035A discloses the preparation method of the lithium titanate of a kind of alumina-coated, comprises the following steps 1): will
Aluminium salt, lithium titanate, the first alcohols solvent and dispersant reaction, vacuum drying, obtain the lithium titanate precursor of aluminium salt cladding；
The mass ratio of described lithium titanate and the first alcohols solvent is 1:0.5～1:4；2) lithium titanate precursor described aluminium salt being coated with burns
Knot cooling, obtains the lithium titanate of alumina-coated.Do so can reduce Ti-O key to a certain extent and divide the catalysis of electrolyte
Solution effect, thus play the effect improving battery flatulence.But owing to aluminium oxide belongs to indifferent oxide and non-conductive, therefore can reduce
The monolithic conductive performance of material, the rate charge-discharge performance eventually making material is the best.
Summary of the invention
The problems referred to above existed in view of prior art, it is an object of the invention to provide a kind of high-performance titanium-containing oxide,
Its preparation method and the purposes as negative material, this negative material electric conductivity is preferable, and tap density is higher, the number of conductivity
Magnitude is 10-3～10-2S/cm, tap density is 1.3～2.0g/cm3, the battery made as negative pole using this titanium-containing oxide
High rate capability and cycle performance are excellent, under the high magnification of 10C and 20C charge specific capacity respectively at more than 168mAh/g and
More than 160mAh/g, circulates 2000 times under the conditions of the discharge and recharge of 10C, and capability retention is more than 98.1%.And the present invention
The preparation technology of method simple, easily operate, energy consumption is low, it is easy to industrialization, and the material prepared can be widely used in height
The Power capacitor industry of power density needs.
" high-performance " in " high-performance titanium-containing oxide " of the present invention refers to: similar compared to sell in the market
Type or similar product, the titanium-containing oxide in the present invention has more high rate capability, more excellent following as battery cathode
Ring performance, under the high magnification of 10C and 20C, charge specific capacity is respectively at more than 168mAh/g and more than 160mAh/g, 10C's
Circulating 2000 times under the conditions of discharge and recharge, capability retention is more than 98.1%.
To achieve these goals, the present invention is by the following technical solutions:
First aspect, the invention provides a kind of titanium-containing oxide, and described titanium-containing oxide includes: lithium titanate particle, with
And it is coated on the conductive network film on lithium titanate particle surface, wherein, the chemical composition of described conductive network film is boride, nitridation
Any one or the combination of at least two in thing or carbide.
Preferably, the tap density of described titanium-containing oxide is 1.3～2.0g/cm3, such as, can be 1.3g/cm3、
1.35g/cm3、1.4g/cm3、1.43g/cm3、1.46g/cm3、1.5g/cm3、1.6g/cm3、1.62g/cm3、
1.71g/cm3、1.89g/cm3、1.97g/cm3Or 2.0g/cm3Deng.
Preferably, the order of magnitude of the conductivity of described titanium-containing oxide is 10-3～10-2S/cm, such as, can be 1 × 10-3S/
cm、3×10-3S/cm、5×10-3S/cm、8×10-3S/cm、1×10-2S/cm、2×10-2S/cm、3×10-2S/cm、5×10- 2S/cm、6×10-2S/cm、8×10-2S/cm or 9 × 10-2S/cm etc..
Preferably, the chemical composition of described boride is TiB2-xOr MgB2-xIn any one or the combination of both,
And 0≤x≤2.
Preferably, the chemical composition of described nitride is TiN or TiNOxIn any one or the combination of both, and 1
≤x≤3。
Preferably, the chemical composition of described carbide is TiC, SiC1+x, any one or both in TaC or NbC
Combination, and 0≤x≤3.
Preferably, it is 0.5～10% that described conductive network film accounts for the mass percent of titanium-containing oxide, such as, can be
0.5%, 0.8%, 1%, 1.5%, 2%, 2.3%, 2.6%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%
Or 10% etc., preferably 1.5～3%.
Preferably, the particle diameter of described lithium titanate particle is 0.2 μm～10 μm, can be such as 0.2 μm, 0.5 μm, 1 μm, 2 μm,
2.5 μm, 3.5 μm, 5 μm, 6 μm, 8 μm, 8.5 μm, 9 μm or 10 μm etc..
Preferably, the thickness of described conductive network film is 0.03 μm～0.6 μm, can be such as 0.03 μm, 0.04 μm, 0.05
μm, 0.06 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm, 0.5 μm or 0.6 μm etc..
In the titanium-containing oxide of the present invention, described conductive network film even compact, described conductive network film is tight and equal
It is coated on lithium titanate particle surface evenly.
Owing to the titanium-containing oxide of the present invention is the conductive network film fine and close by lithium titanate particle coated with uniform one layer
Material is constituted, the conductive network that this and lithium titanate is combined closely and formed, thin unlike traditional carbons conductive material
Pine, its density is also bigger than traditional carbons material, thus is applied in battery show more advantage as negative material,
The tap density of such as material is big, and then the volume energy of battery can be made significantly to be promoted；It addition, this layer of conductive network
Film is combined closely with lithium titanate, and overpotential is relatively low therebetween, and there is strong chemical bond, such that it is able to preferably
Improve the electronic conductivity of this negative material, reduce the internal resistance of negative material and improve the high rate capability of battery.
Second aspect, the invention provides a kind of chemical vapor deposition unit using improvement and prepares as described in relation to the first aspect
The method of titanium-containing oxide, the chemical vapor deposition unit of described improvement includes:
Electric furnace 1, microwave device 11, storing treatment bench 111, power supply 2, gas access A, conductive agent presoma entrance B and acid
Entrance C, wherein, described microwave device 11 is arranged on the inside of described electric furnace 1, described carrier gas inlet A, conductive agent presoma entrance
B is connected by pipeline 3 with electric furnace 1 respectively with acid entrance C；
Wherein, the described method using the chemical vapor deposition unit improved to prepare described titanium-containing oxide includes following step
Rapid:
(I) lithium titanate is placed on the storing treatment bench 111 in electric furnace 1, to electric furnace 1, is passed through acid and load from acid entrance C
The mixture of gas, carries out acidification to lithium titanate；
(II) close acid entrance C, be made up of noble gas and reducibility gas to electric furnace 1 is passed through from gas access A
Mixed gas, to discharge the mixture of the acid in electric furnace 1 and carrier gas, then makes the microwave device 11 in electric furnace 1 heat up；
(III) to microwave device 11, it is passed through conductive agent presoma from conductive agent presoma entrance B, carries out vapour deposition,
To titanium-containing oxide.
Microwave device 11 in the present invention is arranged on the inside of electric furnace 1, and is internally provided with storing at microwave device 11
Treatment bench, when microwave device carries out vapour deposition, the molecule ionization of reacting gas, substrate deposits, namely microwave occurs
Plasma activated chemical vapour deposition.
Preferably, described storing treatment bench 111 is snakelike storing treatment bench, can increase lithium titanate matrix and reacting gas
Contact area, improve contact conditions, so that matrix material is combined finer and close with conducting membrane material, evenly.
Preferably, the chemical vapor deposition unit of described improvement also includes being arranged between connection acid entrance C and electric furnace 1
Carburator 4 on pipeline 3, this carburator 4 can make the mixture of acid and the carrier gas entered from acid entrance C be vaporized into gaseous state, should
The acid of gaseous state and the mixture of carrier gas are entered in microwave device 11 by pipeline 3.
Preferably, the chemical vapor deposition unit of described improvement also include being arranged on connection conductive agent presoma entrance B with
The carburator 4 on pipeline 3 between electric furnace 1, this carburator 4 can make from conductive agent presoma entrance B enter liquid or
The conductive agent presoma of molten state and the mixture of carrier gas are vaporized into gaseous state, the conductive agent presoma of this gaseous state and the mixing of carrier gas
Thing is in pipeline 3 enters microwave device 11.
Preferably, the chemical vapor deposition unit of described improvement also includes air valve 5, air gauge 6 and being arranged on pipeline 3
Effusion meter 7.
Preferably, the chemical vapor deposition unit of described improvement also includes vacuum pump 8 and the tail gas recycle being connected with electric furnace 1
Device 9.
Preferably, the power supply 2 in the chemical vapor deposition unit of described improvement is DC source, the maximum work of described power supply
Rate is 5KW.
The chemical vapor deposition unit of the improvement in the present invention be specific to the titanium-containing oxide of the present invention preparation and
Design.The uniqueness of assembly of the invention points out to be mainly reflected in 2 points:
One of advantage is assembly of the invention by increasing acid entrance, and lithium titanate matrix can carry out acid treatment in advance,
Be possible not only to increase the bond strength of conducting membrane material that matrix obtains with deposition, but also can improve the conducting film that obtains with
Compactness that matrix combines and the uniformity, solve during vapour deposition of the prior art can only process targetedly breakthroughly
Property or acid material matrix on the weak side, and can not be in the problem of the overbased materials surface high effective deposition conducting films such as lithium titanate.
The two of advantage be assembly of the invention by being designed with snakelike storing treatment bench, lithium titanate matrix can be made and lead
The combination of electrolemma is finer and close, evenly.
In the present invention, by acid and the mixture of carrier gas and contacting of lithium titanate matrix, lithium titanate surface shape can be removed
The oxygen-containing functional group that become or absorption produces.
Preferably, the method using the chemical vapor deposition unit improved to prepare described titanium-containing oxide of the present invention
In, described in step (I) in the mixture of acid and carrier gas, described acid is volatile anhydrous small molecular organic acid, preferably first
Any one or the mixture of at least two in acid, acetic acid, propanoic acid, acrylic acid or acetic anhydride.
Preferably, in the mixture of described acid and carrier gas, described carrier gas is nitrogen, argon, helium, neon, Krypton or xenon
Any one or the mixture of at least two in gas.
Preferably, in step (I), the mixture of described acid and carrier gas after acid entrance C enters, arrive electric furnace 1 it
Before, through carburator 4.
Preferably, the quality of the titanium-containing oxide to prepare is in terms of 100 parts, the quality of step (I) described lithium titanate
Part be 90～99.5 parts, can be such as 90 parts, 91 parts, 92 parts, 92.5 parts, 93.5 parts, 94 parts, 95 parts, 96 parts, 97 parts, 97.5
Part, 98 parts, 99 parts, 99.2 parts or 99.5 parts etc..
Preferably, the time of step (I) described acidification is 1～10h, can be such as 1h, 2h, 3h, 3.5h, 4.5h,
5h, 6h, 7h, 8h, 9h or 10h etc..
Preferably, being passed through of step (II) described carrier gas is carried out at normal temperatures and pressures.
Heretofore described " normal temperature and pressure " refers to: pressure is a normal atmosphere, temperature in the range of 15～35 DEG C,
Temperature for example, 15 DEG C, 18 DEG C, 20 DEG C, 22 DEG C, 25 DEG C, 28 DEG C, 30 DEG C, 32 DEG C, 34 DEG C or 35 DEG C etc..
Preferably, in the described carrier gas being made up of noble gas and reducibility gas of step (II), described noble gas is
Any one or the mixture of at least two in nitrogen, argon, helium, neon, Krypton or xenon.
Preferably, in the described carrier gas being made up of noble gas and reducibility gas of step (II), described reducibility gas
For hydrogen.
Preferably, step (II) makes the microwave device 11 in described electric furnace 1 be warming up to 200～900 DEG C, such as, can be 200
℃、225℃、240℃、260℃、290℃、320℃、350℃、400℃、425℃、460℃、485℃、510℃、540℃、
580 DEG C, 625 DEG C, 675 DEG C, 820 DEG C, 855 DEG C or 900 DEG C etc..
In the present invention, step (III) described conductive agent presoma is gaseous state, liquid or solid-state.
Preferably, when described conductive agent presoma is gaseous state, the conductive agent presoma of gaseous state enters from presoma entrance B
Enter, in piping 3 is directly entered microwave device 11.
Preferably, when described conductive agent presoma is gaseous state, the conductive agent presoma of gaseous state be passed through speed be 10～
200mL/min, can be such as 10mL/min, 20mL/min, 30mL/min, 50mL/min, 80mL/min, 100mL/min,
125mL/min, 150mL/min, 165mL/min, 185mL/min or 200mL/min etc..
Preferably, when described conductive agent presoma is liquid, the conductive agent presoma of liquid is carried by carrier gas, before entrance
Driving body entrance B, be then passed through carburator 4 and become gaseous state, the conductive agent presoma of the gaseous state obtained and the mixture of carrier gas are through pipe
Road 3 enters in microwave device 11.
Preferably, when described conductive agent presoma is solid-state (can be such as the solid of low melting point), first by solid-state
The heating of conductive agent presoma obtains the conductive agent presoma of molten state, and then the conductive agent presoma of molten state is entrained into by carrier gas
Enter presoma entrance B, then become gaseous state through carburator 4, the conductive agent presoma of the gaseous state obtained and the mixture warp of carrier gas
Pipeline 3 enters in microwave device 11.
Preferably, the carrier gas carrying the conductive agent presoma of described liquid or the conductive agent presoma of described molten state is independent
Ground is any one or the mixed gas of at least two, being passed through of carrier gas in nitrogen, argon, helium, neon, Krypton or xenon
Speed independently be preferably 50～300mL/min, can be such as 50mL/min, 60mL/min, 80mL/min, 100mL/min,
125mL/min、150mL/min、170mL/min、200mL/min、220mL/min、245mL/min、265mL/min、280mL/
Min or 300mL/min etc..
Preferably, described conductive agent presoma is made up of the first conductive agent presoma and the mixing of the second conductive agent presoma
, wherein, the first conductive agent presoma is any one or the mixture of at least two in borine, carbons hydrocarbon or ammonia,
Two conductive agent presomas are any one or at least two in metallic alkoxide compound, silane, Metal Substrate alkane or titanate esters
Mixture.
Preferably, any one or at least two during described borine includes diborane, tetraborane, pentaborane or own borine
Mixture, but be not limited to the above-mentioned borine enumerated, other borines that can reach effect of the present invention can also be used for this
Bright.
Preferably, what described carbons hydrocarbon included in methane, ethane, propane, butane, ethylene, propylene, acetylene or propine is any
A kind of or the mixture of at least two, but the carbons hydrocarbon enumerated described in being not limited to, other are up to the carbon of effect of the present invention
Class alkane can also be used for the present invention.
Preferably, any one during described metallic alkoxide compound includes ethanol niobium, Diethoxymagnesium, methanol tantalum or ethanol tantalum
Or the mixture of at least two, but the metallic alkoxide compound enumerated described in being not limited to, other are up to effect of the present invention
Metallic alkoxide compound can also be used for the present invention.
Preferably, any one during described silane includes monosilane, Disilicoethane, tri isopropyl silane or tetramethylsilane
Or the mixture of at least two, but the silane enumerated described in being not limited to, other also may be used up to the silane of effect of the present invention
For the present invention.
Preferably, any one during described titanate esters includes butyl titanate, tetraethyl titanate or tetraisopropyl titanate
Or the mixture of at least two, but the titanate esters enumerated described in being not limited to, other are up to the titanate esters of effect of the present invention
Can also be used for the present invention.
Preferably, the time of step (III) described vapour deposition is 0.5～5h, can be such as 0.5h, 0.8h, 1h, 1.2h,
1.5h, 2h, 2.5h, 2.7h, 3h, 3.2h, 3.5h, 4h, 4.5h or 5h etc.
Preferably, the quality of the titanium-containing oxide to prepare is in terms of 100 parts, deposits at lithium titanate particle surface vapor
The weight portion of conductive network film be 0.5～10 part.
Preferably, described method is additionally included in after step (III) vapour deposition completes, and carries out the step of cooling down.
The method using the chemical vapor deposition unit improved to prepare titanium-containing oxide of the present invention has preparation work
Skill is simple, processing ease, energy consumption are low and is prone to the advantage of industrialization, and, employing the method, will not to lithium titanate surface modification
Affect the crystal structure of lithium titanate itself, it can be ensured that battery or the more preferable cycle performance of electric capacity.
The third aspect, the present invention provides the purposes of titanium-containing oxide as described in relation to the first aspect, and described titanium-containing oxide is used
Make negative material, can be widely applied to battery or the Power capacitor industry of high power density demand.
Compared with the prior art, the method have the advantages that
(1), in the titanium-containing oxide of the present invention, fine and close conductive network film is closely combined in the surface of lithium titanate particle,
This structure is loose unlike traditional carbons conductive material, and the density of fine and close conductive network film is compared to tradition carbons material
Material is bigger, and the titanium-containing oxide of the present invention is applied to battery as negative material and has more advantage, such as tap density greatly,
The volume energy that can make battery is increased dramatically；Conductive network film is combined closely with lithium titanate, and the overpotential of the two is relatively low,
And there is therebetween strong chemical bond, can preferably improve the electronic conductivity of negative material, reduce negative pole material
The internal resistance expected the high rate capability and the cycle performance that improve battery, the battery that the titanium-containing oxide of the present invention is made as negative pole
Under the high magnification of 10C and 20C, charge specific capacity is respectively at more than 168mAh/g and more than 160mAh/g, at 10C discharge and recharge bar
Circulating 2000 times under part, capability retention is more than 98.1%.
(2) chemical vapor deposition unit improved that uses of the present invention is prepared in the method for titanium-containing oxide, the dress of use
Put and there is following innovative point: one is assembly of the invention by increasing acid entrance, can carry out lithium titanate matrix in advance at acid
Reason, is possible not only to increase the bond strength of the conducting membrane material that matrix obtains with deposition, but also can improve the conduction obtained
Compactness that film is combined with matrix and the uniformity, solving vapour deposition of the prior art can only locate breakthroughly targetedly
Manage neutral or on the weak side acid material matrix, and can not be in the problem of the overbased materials surface high effective deposition conducting films such as lithium titanate.
Two be assembly of the invention by being designed with snakelike storing treatment bench, lithium titanate matrix can be made more to cause with the combination of conducting film
Close, evenly.
(3) method using the chemical vapor deposition unit improved to prepare titanium-containing oxide of the present invention has following excellent
Point: technique simple operations is easy, and energy consumption is low, it is easy to industrialized production；And, use the method to lithium titanate surface modification system
Standby titanium-containing oxide, will not cause the phenomenon of changes in crystal structure, the present invention as method of modifying such as the element dopings of prior art
Method do not interfere with the crystal structure of lithium titanate itself, it can be ensured that battery or the more preferable cycle performance of electric capacity.
Accompanying drawing explanation
Fig. 1 is the structural representation of the chemical vapor deposition unit after improving, and wherein, reference is as follows:
1-electric furnace 11-microwave device 111-storing treatment bench 2-power supply
A-gas access B-conducts electricity presoma entrance C-acid entrance
3-pipeline 4-carburator 5-air valve 6-Pressure gauge
7-effusion meter 8-vacuum pump 9-device for recovering tail gas；
Fig. 2 a and Fig. 2 b is SEM figure and the tangent plane SEM figure of the titanium-containing oxide that the embodiment of the present invention 1 prepares respectively；
Fig. 3 is the titanium-containing oxide for preparing using the embodiment of the present invention 1 is prepared as battery as negative material, and
The charging and discharging curve figure that under 10C multiplying power, discharge and recharge obtains.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
The titanium-containing oxide prepared using embodiment 1-4 and the sample of comparative example 1-3 as negative material identical
Under the conditions of prepare battery and test its chemical property, the preparation method of concrete battery is as follows: by negative material, conductive agent charcoal
Black and Kynoar (PVDF) presses the part by weight mix homogeneously of 82:10:8, is applied on Copper Foil colelctor electrode, vacuum dried case
Dry for standby, simulated battery is assemblied in the glove box of applying argon gas and carries out, and electrolyte is for being 1mol/L LiPF6/EC+DMC+EMC
Solution, wherein the volume ratio of EC, DMC and EMC is 1:1:1, and metal lithium sheet is to electrode, uses conventional production process to be assembled into electricity
Pond.
Electrochemical property test is carried out on new prestige battery performance test instrument, and discharge and recharge scope is 1.0V to 2.5V, charge and discharge
Electricity multiplying power is 1C, 10C and 20C.
Embodiment 1
The chemical vapor deposition unit of a kind of improvement, the structural representation of the chemical vapor deposition unit of described improvement is shown in figure
1, described device includes electric furnace 1, microwave device 11, storing treatment bench 111, power supply 2, gas access A, conductive agent presoma entrance
B and acid entrance C, wherein, described microwave device 11 is arranged on the inside of described electric furnace 1, described carrier gas inlet A, conductive agent forerunner
Body entrance B is connected by pipeline 3 with electric furnace 1 respectively with acid entrance C.
A kind of method that chemical vapor deposition unit using above-mentioned improvement prepares titanium-containing oxide, described method includes
Following steps:
(I) 1000g lithium titanate is placed on the storing treatment bench 111 in electric furnace 1, opens acid entrance C and be passed through in electric furnace 1
The acid of gaseous state and the mixture of carrier gas, be fully contacted with lithium titanate, and lithium titanate carries out acidification, closes acid entrance C, treats acid
After change processes 3h, open gas access A, in electric furnace 1, be passed through the mixed gas being made up of noble gas and reducibility gas, with
Discharge unnecessary acid and the mixture of carrier gas in electric furnace 1, then make the microwave device 11 in electric furnace 1 be warming up to 300 DEG C, open and lead
Electricity agent presoma entrance B is passed through methane and silane with the speed of 100mL/min and 200mL/min in microwave device 11 respectively,
Vapour deposition 3h, cooling, obtain titanium-containing oxide, described titanium-containing oxide is by lithium titanate particle and is coated on lithium titanate particle table
The SiC in face1+xConstitute, and SiC1+xThe mass percent accounting for titanium-containing oxide is 2.3%.
After tested, the conductivity of the titanium-containing oxide that the present embodiment prepares is 8.1 × 10-3S/cm, tap density is
1.4g/cm3。
Fig. 2 a and Fig. 2 b is SEM figure and the tangent plane SEM figure of the titanium-containing oxide that the present embodiment 1 prepares respectively, by scheming
It can be seen that lithium titanate particle smooth surface, SiC1+xIt is coated on the surface of lithium titanate particle uniformly.
Fig. 3 is the titanium-containing oxide for preparing using the present embodiment 1 is prepared as simulated battery as negative material, and
The charging and discharging curve figure that under 10C multiplying power, discharge and recharge obtains, the voltage of gained battery is about 1.5V as seen from the figure, reversible specific capacity
Reach 170mAh/g, for more than the 97% of theoretical specific capacity.
The high rate capability of the battery that the titanium-containing oxide negative material of the present embodiment is made is the most excellent, at 10C and 20C
Charge specific capacity be respectively 170mAh/g and 162mAh/g, cycle performance of battery is the most excellent, under the conditions of 10C discharge and recharge
Circulating 2000 times, capability retention reaches 99.4%.
Embodiment 2
The chemical vapor deposition unit of a kind of improvement, described device includes that electric furnace 1, microwave device 11, snakelike storing process
Platform 111, power supply 2, gas access A, conductive agent presoma entrance B, acid entrance C and carburator 4, wherein, described microwave device 11
It is arranged on the inside of described electric furnace 1, described carrier gas inlet A, conductive agent presoma entrance B and acid entrance C to pass through with electric furnace 1 respectively
Pipeline 3 is connected；Carburator 4 be separately positioned on connection conductive agent presoma entrance B with on the pipeline 3 of electric furnace 1 and be connected acid and enter
On the pipeline 3 of mouth C and electric furnace 1.
A kind of method that chemical vapor deposition unit using above-mentioned improvement prepares titanium-containing oxide, described method includes
Following steps:
(I) 1000g lithium titanate is placed on the storing treatment bench 111 in electric furnace 1, opens acid entrance C and be passed through in electric furnace 1
Acid and the mixture of carrier gas, make this mixture become gaseous state through carburator 4, flow through pipeline 3, be fully contacted with lithium titanate, right
Lithium titanate carries out acidification, closes acid entrance C, after acidification 4h, opens gas access A, be passed through by lazy in electric furnace 1
Property gas and the mixed gas that constitutes of reducibility gas, discharge unnecessary acid and the mixture of carrier gas in electric furnace 1, then make electric furnace
Microwave device 11 in 1 is warming up to 500 DEG C；Open conductive agent presoma entrance B in microwave device, be passed through ammonia, and pass through
The butyl titanate (liquid) that noble gas argon carries, wherein ammonia is passed through speed is 150mL/min, and noble gas argon leads to
Entering speed is 250mL/min, and the material entered from conductive agent presoma entrance B becomes gaseous state through carburator 4, and reacting gas enters
Enter vapour deposition 2h in microwave device, after material cools down, obtain titanium-containing oxide, this titanium-containing oxide by lithium titanate particle and
The TiN being coated on lithium titanate particle surface is constituted, and TiN to account for the mass percent of titanium-containing oxide be 1.8%.
After tested, the conductivity of the titanium-containing oxide that the present embodiment prepares is 6.9 × 10-3S/cm, tap density is
1.3g/cm3。
The high rate capability of the battery that the titanium-containing oxide negative material of the present embodiment is made is the most excellent, at 10C and 20C
High magnification under charge specific capacity respectively reached 168mAh/g and 160mAh/g, circulate under the conditions of 10C discharge and recharge simultaneously
2000 times, capability retention reaches 98.6%.
Embodiment 3
The chemical vapor deposition unit of a kind of improvement, described device includes that electric furnace 1, microwave device 11, snakelike storing process
Platform 111, power supply 2, gas access A, conductive agent presoma entrance B, acid entrance C and carburator 4, wherein, described microwave device 11
It is arranged on the inside of described electric furnace 1, described carrier gas inlet A, conductive agent presoma entrance B and acid entrance C to pass through with electric furnace 1 respectively
Pipeline 3 is connected；Carburator 4 be separately positioned on connection conductive agent presoma entrance B with on the pipeline 3 of electric furnace 1 and be connected acid and enter
On the pipeline 3 of mouth C and electric furnace 1.
A kind of method that chemical vapor deposition unit using above-mentioned improvement prepares titanium-containing oxide, described method includes
Following steps:
(I) 2000g lithium titanate is placed on the storing treatment bench 111 in electric furnace 1, opens acid entrance C and be passed through in electric furnace 1
Acid and the mixture of carrier gas, make this mixture become gaseous state through carburator 4, flow through pipeline 3, be fully contacted with lithium titanate, right
Lithium titanate carries out acidification, closes acid entrance C, after acidification 6h, opens gas access A, be passed through by lazy in electric furnace 1
Property gas and the mixed gas that constitutes of reducibility gas, discharge unnecessary acid and the mixture of carrier gas in electric furnace 1, then make electric furnace
Microwave device 11 in 1 is warming up to 800 DEG C；Open conductive agent presoma entrance B in microwave device, be passed through diborane (B2H6),
And the tetraethyl titanate (liquid) carried by noble gas argon, wherein diborane is passed through speed is 100mL/min, inertia
It is 250mL/min that gases argon is passed through speed, and the material entered from conductive agent presoma entrance B becomes gaseous state through carburator 4,
Reacting gas enters vapour deposition 3.5h in microwave device, obtains titanium-containing oxide after material cools down, this titanium-containing oxide by
Lithium titanate particle and be coated on the TiB on lithium titanate particle surface2-xConstitute, and TiB2-xAccount for the mass percent of titanium-containing oxide
It is 2.0%.
After tested, the conductivity of the titanium-containing oxide that the present embodiment prepares is 4.7 × 10-2S/cm, tap density is
1.5g/cm3。
The high rate capability of the battery that the titanium-containing oxide negative material of the present embodiment is made is the most excellent, at 10C and 20C
High magnification under charge specific capacity respectively reached 171mAh/g and 163mAh/g, and circulate under the conditions of 10C discharge and recharge
2000 times, capability retention reaches 98.7%.
Embodiment 4
The chemical vapor deposition unit of a kind of improvement, described device includes that electric furnace 1, microwave device 11, snakelike storing process
Platform 111, power supply 2, gas access A, conductive agent presoma entrance B, acid entrance C and carburator 4, the air valve being arranged on pipeline 3,
Vacuum pump 5 and device for recovering tail gas 6, wherein, described microwave device 11 is arranged on the inside of described electric furnace 1；Described carrier gas inlet
A, conductive agent presoma entrance B are connected by pipeline 3 with electric furnace 1 respectively with acid entrance C；Carburator 4 is separately positioned on connection and leads
Electricity agent presoma entrance B with on the pipeline 3 of electric furnace 1 and is connected on the pipeline 3 of sour entrance C and electric furnace 1；Vacuum pump 5 and tail gas
Retracting device 6 is connected with electric furnace 1 respectively.
A kind of method that chemical vapor deposition unit using above-mentioned improvement prepares titanium-containing oxide, described method includes
Following steps:
(I) 1500g lithium titanate is placed on the storing treatment bench 111 in electric furnace 1, opens acid entrance C and be passed through in electric furnace 1
Acid and the mixture of carrier gas, make this mixture become gaseous state through carburator 4, flow through pipeline 3, be fully contacted with lithium titanate, right
Lithium titanate carries out acidification, closes acid entrance C, after acidification 4h, opens gas access A, be passed through by lazy in electric furnace 1
Property gas and the mixed gas that constitutes of reducibility gas, discharge unnecessary acid and the mixture of carrier gas in electric furnace 1, then make electric furnace
Microwave device 11 in 1 is warming up to 600 DEG C；Open conductive agent presoma entrance B in microwave device, be passed through methane, and pass through
Ethanol niobium [Nb (the OC that noble gas argon carries2H5)5], wherein methane is passed through speed is 120mL/min, noble gas argon
Being passed through speed is 200mL/min, and the material entered from conductive agent presoma entrance B becomes gaseous state, reacting gas through carburator 4
Entering vapour deposition 2.5h in microwave device, obtain titanium-containing oxide after material cools down, this titanium-containing oxide is by lithium titanate
Grain and be coated on the NbC on lithium titanate particle surface and constitute, and NbC to account for the mass percent of titanium-containing oxide be 2.7%.
After tested, the conductivity of the titanium-containing oxide that the present embodiment prepares is 5.9 × 10-2S/cm, tap density is
1.5g/cm3。
The high rate capability of the battery that the titanium-containing oxide negative material of the present embodiment is made is the most excellent, at 10C and 20C
High magnification under charge specific capacity respectively reached and circulated 2000 times under the conditions of 169mAh/g and 164mAh/g, 10C discharge and recharge, hold
Amount conservation rate reaches 98.1%.
Comparative example 1
Vapor phase growing apparatus of the prior art is used to prepare titanium-containing oxide, specific as follows:
Being placed on the treatment bench of vapor phase growing apparatus by 1000g lithium titanate, then device is warming up to 300 DEG C；To reacting furnace
Being passed through methane and monosilane conductive agent presoma atmosphere in Nei, wherein methane is passed through speed is 100mL/min, and silane is passed through speed
For 200mL/min, vapour deposition 3h, after material cools down, obtain titanium-containing oxide, this titanium-containing oxide by lithium titanate particle and
It is coated on the SiC on lithium titanate particle surface1+xConstitute, and SiC1+xThe mass percent accounting for titanium-containing oxide is 0.6%.
After tested, the conductivity of the titanium-containing oxide that this comparative example prepares is 3.4 × 10-7S/cm, tap density is
0.97g/cm3。
The battery that the titanium-containing oxide negative material of the present embodiment is made charge specific capacity under 10C and 20C high magnification divides
Do not reach 137mAh/g and 110mAh/g.
Comparative example 2
Vapor phase growing apparatus of the prior art is used to prepare titanium-containing oxide, specific as follows:
Being placed on the treatment bench of vapor phase growing apparatus by 2000g lithium titanate, then device is warming up to 800 DEG C；To reacting furnace
Diborane (B it is passed through in Nei2H6), and transport tetraethyl titanate (liquid) by noble gas argon, wherein diborane is passed through speed
Rate is 100mL/min, and it is 250mL/min that noble gas argon is passed through speed, vapour deposition 3.5h, obtains titanium after material cools down
Being oxide, this titanium-containing oxide is by lithium titanate particle and the TiB that is coated on lithium titanate particle surface2-xConstitute, and TiB2-xAccount for
The mass percent of titanium-containing oxide is 0.9%.
After tested, the conductivity of the titanium-containing oxide that this comparative example prepares is 2.8 × 10-7S/cm, tap density is
0.96g/cm3。
The battery that the titanium-containing oxide negative material of the present embodiment is made charge specific capacity under 10C and 20C high magnification divides
Do not reach 133mAh/g and 109mAh/g.
Comparative example 3
Taking pure phase lithium titanate sample directly to test, its tap density is 0.9g/cm3, conductivity is 4.5 × 10-8S/
Cm, under 10C and 20C high magnification, charge specific capacity has respectively reached 116mAh/g and 94mAh/g.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. a titanium-containing oxide, it is characterised in that described titanium-containing oxide includes lithium titanate particle, and is coated on lithium titanate
The conductive network film of particle surface, wherein, the chemical composition of described conductive network film is in boride, nitride or carbide
Any one or the combination of at least two.
Titanium-containing oxide the most according to claim 1, it is characterised in that the tap density of described titanium-containing oxide is 1.3
～2.0g/cm3；
Preferably, the order of magnitude of the conductivity of described titanium-containing oxide is 10-3～10-2S/cm；
Preferably, the chemical composition of described boride is TiB2-xOr MgB2-xIn any one or the combination of both, and 0≤
x≤2；
Preferably, the chemical composition of described nitride is TiN or TiNOxIn any one or the combination of both, and 1≤x≤
3；
Preferably, the chemical composition of described carbide is TiC, SiC1+x, any one or the group of both in TaC or NbC
Close, and 0≤x≤3；
Preferably, it is 0.5～10% that described conductive network film accounts for the mass percent of titanium-containing oxide, preferably 1.5～3%；
Preferably, the particle diameter of described lithium titanate particle is 0.2 μm～10 μm；
Preferably, the thickness of described conductive network film is 0.03 μm～0.6 μm.
3. the chemical vapor deposition unit using improvement prepares a method for titanium-containing oxide as claimed in claim 1 or 2,
It is characterized in that, the chemical vapor deposition unit of described improvement includes: electric furnace (1), microwave device (11), storing treatment bench
(111), power supply (2), gas access (A), conductive agent presoma entrance (B) and acid entrance (C), wherein, described microwave device
(11) being arranged on the inside of described electric furnace (1), described storing treatment bench (111) is arranged on the inside of described microwave device (11),
Described gas access (A), conductive agent presoma entrance (B) are connected by pipeline (3) with electric furnace (1) respectively with acid entrance (C)；
Wherein, the described method using the chemical vapor deposition unit improved to prepare described titanium-containing oxide comprises the following steps:
(I) lithium titanate is placed on the storing treatment bench (111) in electric furnace (1), to electric furnace (1), is passed through acid from acid entrance (C)
With the mixture of carrier gas, lithium titanate is carried out acidification；
(II) close acid entrance (C), be made up of noble gas and reducibility gas to electric furnace (1) is passed through from gas access (A)
Mixed gas, to discharge the mixture of the acid in electric furnace 1 and carrier gas, then make the microwave device (11) in electric furnace (1) heat up；
(III) to microwave device (11), it is passed through conductive agent presoma from conductive agent presoma entrance (B), carries out vapour deposition,
To titanium-containing oxide.
Method the most according to claim 3, it is characterised in that described storing treatment bench (111) is snakelike storing treatment bench；
Preferably, the chemical vapor deposition unit of described improvement also include being separately positioned on connection acid entrance (C) and electric furnace (1) it
Between pipeline (3) upper and connect the carburator (4) on the pipeline (3) between conductive agent presoma entrance (B) and electric furnace (1)；
Preferably, the chemical vapor deposition unit of described improvement also includes air valve (5), the Pressure gauge (6) being arranged on pipeline (3)
With effusion meter (7)；
Preferably, the chemical vapor deposition unit of described improvement also includes vacuum pump (8) and the tail gas recycle being connected with electric furnace (1)
Device (9).
5. require the method described in 3 or 4 according to power, it is characterised in that described power supply (2) is DC source, described power supply (2)
Peak power is 5KW.
6. according to the method described in any one of claim 3-5, it is characterised in that the chemical gaseous phase deposition dress that described employing improves
Put in the method preparing described titanium-containing oxide, in the mixture of described acid and carrier gas, described acid be volatile little molecule without
Any one or the mixture of at least two in water organic acid, preferably formic acid, acetic acid, propanoic acid, acrylic acid or acetic anhydride；
Preferably, in the mixture of described acid and carrier gas, described carrier gas is in nitrogen, argon, helium, neon, Krypton or xenon
Any one or the mixture of at least two；
Preferably, in step (I), described sour gas is before acid entrance (C) enters into electric furnace (1), through carburator
(4)；
Preferably, the quality of the titanium-containing oxide to prepare is in terms of 100 parts, and the mass parts of step (I) described lithium titanate is
90～99.5 parts；
Preferably, the time of step (I) described acidification is 1～10h.
7. according to the method described in any one of claim 3-6, it is characterised in that being passed through of step (II) described mixed gas
Carry out under normal temperature and pressure；
Preferably, in the described mixed gas being made up of noble gas and reducibility gas of step (II), described noble gas is
Any one or the mixture of at least two in nitrogen, argon, helium, neon, Krypton or xenon；
Preferably, in the described mixed gas being made up of noble gas and reducibility gas of step (II), described reducibility gas
For hydrogen；
Preferably, the microwave device (11) in step (II) makes described electric furnace (1) is warming up to 200～900 DEG C.
8. according to the method described in any one of claim 3-7, it is characterised in that step (III) described conductive agent presoma is gas
State, liquid or solid-state；
Preferably, when described conductive agent presoma is gaseous state, the conductive agent presoma of gaseous state enters from presoma entrance (B),
In piping (3) enters into microwave device (11)；
Preferably, when described conductive agent presoma is gaseous state, the conductive agent presoma of gaseous state be passed through speed be 10～
200mL/min；
Preferably, when described conductive agent presoma is liquid, the conductive agent presoma of liquid is carried by carrier gas, enters presoma
Entrance (B), is then passed through carburator (4) and becomes gaseous state, and the conductive agent presoma of the gaseous state obtained and the mixture of carrier gas are through pipe
Road (3) enters in microwave device (11)；
Preferably, when described conductive agent presoma is solid-state, first the conductive agent presoma of solid-state is heated and obtain molten state
Conductive agent presoma, then the conductive agent presoma of molten state is carried along into presoma entrance (B) by carrier gas, then through carburator
(4) becoming gaseous state, the conductive agent presoma of the gaseous state obtained and the mixture of carrier gas enter microwave device (11) through pipeline (3)
In；
Preferably, the carrier gas of the conductive agent presoma of described liquid or the conductive agent presoma of described or molten state is carried independently
For any one in nitrogen, argon, helium, neon, Krypton or xenon or the mixed gas of at least two, carrier gas be passed through speed
Rate is preferably 50～300mL/min independently；
Preferably, described conductive agent presoma is mixed by the first conductive agent presoma and the second conductive agent presoma and forms,
Wherein, the first conductive agent presoma is any one or the mixture of at least two in borine, carbons hydrocarbon or ammonia, and second leads
Electricity agent presoma is any one or the mixture of at least two in metallic alkoxide compound, silane or titanate esters；
Preferably, any one or at least two during described borine includes diborane, tetraborane, pentaborane or own borine mixed
Compound；
Preferably, described carbons hydrocarbon includes any one in methane, ethane, propane, butane, ethylene, propylene, acetylene or propine
Or the mixture of at least two；
Preferably, during described metallic alkoxide compound includes ethanol niobium, Diethoxymagnesium, methanol tantalum or ethanol tantalum any one or extremely
The mixture of few two kinds；
Preferably, during described silane includes monosilane, Disilicoethane, tri isopropyl silane or tetramethylsilane any one or extremely
The mixture of few two kinds；
Preferably, during described titanate esters includes butyl titanate, tetraethyl titanate or tetraisopropyl titanate any one or extremely
The mixture of few two kinds.
9. according to the method described in any one of claim 3-8, it is characterised in that the time of step (III) described vapour deposition is
0.5～5h；
Preferably, the quality of the titanium-containing oxide to prepare is in terms of 100 parts, leading of lithium titanate particle surface vapor deposition
The weight portion of electric network film is 0.5～10 part；
Preferably, described method is additionally included in after step (III) vapour deposition completes, and carries out the step of cooling down.
10. the purposes of a titanium-containing oxide as claimed in claim 1 or 2, it is characterised in that described titanium-containing oxide is used as
Negative material.
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| CN108682852A (en) * | 2018-04-04 | 2018-10-19 | 江西科技师范大学 | A kind of lithium-ion negative pole coating and preparation method |
| CN115786876A (en) * | 2022-10-12 | 2023-03-14 | 厦门中材航特科技有限公司 | Method for preparing tantalum carbide coating by CVD and product thereof |
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