CN109037632A - A kind of nano lithium titanate composite material and preparation method, lithium ion battery - Google Patents
A kind of nano lithium titanate composite material and preparation method, lithium ion battery Download PDFInfo
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- CN109037632A CN109037632A CN201810845322.4A CN201810845322A CN109037632A CN 109037632 A CN109037632 A CN 109037632A CN 201810845322 A CN201810845322 A CN 201810845322A CN 109037632 A CN109037632 A CN 109037632A
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- lithium titanate
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 219
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 218
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 34
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 63
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 21
- 241000446313 Lamella Species 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000006258 conductive agent Substances 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000006837 decompression Effects 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007773 negative electrode material Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- 102000004316 Oxidoreductases Human genes 0.000 claims description 7
- 108090000854 Oxidoreductases Proteins 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 229910003317 GdCl3 Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 claims description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 150000004702 methyl esters Chemical class 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000000470 constituent Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- 229910001947 lithium oxide Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- SXVCBXHAHBCOMV-UHFFFAOYSA-K trichlorogadolinium;hydrate Chemical compound O.[Cl-].[Cl-].[Cl-].[Gd+3] SXVCBXHAHBCOMV-UHFFFAOYSA-K 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- JKXCZYCVHPKTPK-UHFFFAOYSA-N hydrate;trihydrochloride Chemical compound O.Cl.Cl.Cl JKXCZYCVHPKTPK-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 238000002847 impedance measurement Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 thermally conductive Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910014969 LiMnCoO4 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910014340 LiNi1-x-yMnxCoyO2 Inorganic materials 0.000 description 1
- 229910014829 LiNi1−x−yMnxCoyO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 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 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of nano lithium titanate composite materials, the composite material includes lithium titanate nanometer sheet, and it is dispersed in the multi-walled carbon nanotube in the lithium titanate nanometer sheet lamella, in above-mentioned constituent, the mass ratio of the lithium titanate nanometer sheet and the multi-walled carbon nanotube is (3.5-6): 1.The present invention also provides a kind of methods for preparing above-mentioned nano lithium titanate composite material, lithium titanate nanometer sheet is prepared using titanium source, lithium source, conductive agent as raw material, then it is added to the water lithium titanate nanometer sheet and the multi-walled carbon nanotube after nitric acid oxidation to form dispersion liquid A and dispersion liquid B respectively, dispersion liquid A is added in dispersion liquid B, decompression filters after mixing, nano lithium titanate composite material is made in drying.The present invention also provides a kind of lithium ion batteries prepared using above-mentioned nano lithium titanate composite material, and the lithium ion battery energy force density is high, and electrochemical impedance is low, have good chemical property.
Description
Technical field
The invention belongs to lithium ion battery electrode materials to research and develop field, and in particular to a kind of nano barium titanate lithium composite
Material and preparation method thereof, and the lithium ion battery prepared using the nano lithium titanate composite material as electrode material.
Background technique
In recent years, electric car and renewable energy integrating device demand are continuously increased, and have been pushed chargeable, long-lived
Life, high capacity, low cost energy storage device fast development.Lithium ion battery is big with its capacity, the period is long, environmental-friendly etc. excellent
Point becomes a kind of good power source of portable electronic device and electric car.
Lithium ion battery huge number, it is different, it is broadly divided into cylindrical battery and rectangular cell；Although outside lithium battery
There are biggish differences for sight, but the structure composition of battery is very nearly the same, mainly by positive electrode, negative electrode material, electrolyte
It is formed with diaphragm.That presently commercially available positive electrode generallys use is LiCoO2、LiMn2O4、LiNi1-x-yMnxCoyO2、LiFePO4Deng
Lithium-containing compound；Negative electrode material then generally uses the carbon material of various modifications；The medium that electrolyte is transmitted as lithium ion, usually
For LiPF6、LiBF4、LiClO4The solution that equal lithium salts are formed in nonpolar solvent；Diaphragm is usually porous single-layer or multi-layer
High molecular material, lithium ion can selectively shuttle in diaphragm material, while have electronic isolation effect, can be used to
The transmitting of positive and negative interpolar electronics is isolated to prevent short circuit.
In the foundational development of lithium battery, cell positive material, negative electrode material always are the hot spot of research.
LiNi0.5Mn1.5O4、LiMnCoO4、LixCrMnO4Equal positive electrodes, because it is with advantages such as energy density height, operating voltage height,
It is widely popularized；There are also some such as Al2O3, AZO, the coating modifications such as nucleocapsid mechanism positive electrode also developed in succession.
At present be mostly lithium intercalated graphite carbon material in terms of negative electrode material, the material have raw material extensively, price just
Preferably, the advantages that preparation method is simple, functional still can have a series of problems in practical applications, for example, filling for the first time
Discharging efficiency is lower, and volume change is larger in charge and discharge process, and Li dendrite easy to form causes battery short circuit, makes electrolyte
The risk of decomposition is higher, and there are security risks etc..
In contrast, the lithium titanate with spinel structure has excellent performance, as cell negative electrode material, energy
It is enough effectively to overcome above-mentioned carbon material as defect possessed by negative electrode material.Lithium titanate is one kind by lithium metal and low potential transition
The composite oxides of Titanium composition, maximum feature is exactly to have " zero strain ", and lithium ion is being embedded in or is deviating from process
In, lithium titanate lattice constant and volume change all very littles, change rate is within 1%；In charge and discharge cycles, this " zero strain
Property " can be avoided due to stretching back and forth for electrode material and lead to structural damage, to improve the cycle performance of electrode and make
With the service life, circulation bring special capacity fade is reduced, there is extraordinary overcharging resisting, over-discharge feature.
Although lithium titanate has above-mentioned superior function, the characteristic of its own low conductivity makes it in high power charging-discharging
Performance is poor and special capacity fade is very fast, and heavy-current discharge performance is undesirable.By the way that carbon material is carried out compound, system with lithium titanate
It is standby to go out to have both the negative electrode material of the two advantage, it will significantly to promote the service performance of lithium ion battery.Application No. is
The Chinese invention patent of 201310065143.6 entitled " a kind of Lithium-titanate composite negative pole and preparation method thereof ", this is compound
Negative electrode material includes lithium titanate, doped chemical and Graphene/carbon nanotube composite material, effectively prevents graphite in preparation process
Alkene after the drying and with the lamination and agglomeration in lithium titanate recombination process, improve the electrification of lithium titanate composite material
Performance is learned, is had broad application prospects in field of batteries.Application No. is a kind of 201610064687.4 entitled " nano-sheet titaniums
Sour lithium and multi-wall carbon nano-tube composite material and preparation method thereof " Chinese invention patent, with commercially available multi-walled carbon nanotube
(MWCNTs) the modified carbon nanotube in surface is prepared for raw material；It is lithium source using isopropyl titanate as titanium source, lithium hydroxide, divinyl
Triamine is surfactant, and isopropanol and water are solvent, is reacted by surface in situ, prepares nano-sheet lithium titanate and multi wall carbon
Nanometer tube composite materials, the composite material capacity is high, charge-discharge magnification is high, stability is good.In to lithium titanate modifying process, first
By lithium titanate nanosizing, recycles carbon nanotube to be doped lithium titanate, lithium titanate is doped using fluorine ion, to
(preparation of Zhang Pengfei lithium titanate nanometer sheet is with modification and its in lithium-ion electric for the charge-discharge magnification and cycle performance for improving material
The Yangzhou application study [D] in the negative electrode material of pond: Yangzhou University, 2017.).
Although developer has done numerous studies to the modification of lithium titanate/carbon material composite material, and in composite material
Performance improves aspect and has made significant headway, but the preparation process being related in modifying process is often complex, introduces
The risk of impurity is larger.Meanwhile lithium titanate electric conductivity is being improved, and then improve composite charge and discharge rate and cycle performance
Aspect, however it remains very big progress space.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention provides a kind of nano lithium titanate composite materials, this is compound
Material includes lithium titanate nanometer sheet, and the multi-walled carbon nanotube being dispersed in the lithium titanate nanometer sheet lamella, upper
It states in constituent, the mass ratio of the lithium titanate nanometer sheet and the multi-walled carbon nanotube is (3.5-6): 1.Multi-wall carbon nano-tube
After pipe is dispersed in lithium titanate nanometer sheet lamella, there is not agglomeration, has no effect on the sheet of lithium titanate nanometer sheet
Crystal structure, and the nano lithium titanate composite material being combined has good crystallinity, purity is high.Multi-walled carbon nanotube
Large specific surface area, is capable of providing very big contact area, and connection lithium titanate nanometer sheet forms conductive mesh, can effectively improve lithium from
The diffusion velocity and electron-transport speed of son, improve the electrical conduction efficiency of material.Above-mentioned receive is prepared the present invention also provides a kind of
The method of rice lithium titanate composite material, prepares lithium titanate nanometer sheet using titanium source, lithium source, conductive agent as raw material, then respectively by titanium
Sour lithium nanometer sheet and the multi-walled carbon nanotube after nitric acid oxidation are added to the water to form dispersion liquid A and dispersion liquid B, by dispersion liquid A
It is added in dispersion liquid B, decompression filters, is dry after mixing, and nano lithium titanate composite material is made.The present invention also provides one
Kind is using the lithium ion battery of above-mentioned nano lithium titanate composite material preparation, and the lithium ion battery energy density is high, electrochemistry
Impedance is low, has good chemical property.
Present invention technical effect to be achieved is realized by following scheme:
The present invention provides a kind of nano lithium titanate composite materials, are made of lithium titanate nanometer sheet and multi-walled carbon nanotube, described
Multi-walled carbon nanotube is dispersed in the lamella of the lithium titanate nanometer sheet, and the lithium titanate nanometer sheet is received with the multi wall carbon
The mass ratio of mitron is (3.5-6): 1.
Further, the nano lithium titanate composite material is flat crystal structure.
Lithium titanate nanometer sheet has the advantages that " zero strain ", in battery charging and discharging cyclic process, can be avoided due to
Electrode material stretches back and forth and leads to structural damage, to improve the cycle performance and service life of electrode, reduces circulation
Bring special capacity fade has extraordinary overcharging resisting, over-discharge feature, but low conductivity seriously constrains lithium titanate nanometer
The application of piece.Multi-walled carbon nanotube is dispersed in the lamella of lithium titanate nanometer sheet, formed conductive mesh, can effectively improve lithium from
The diffusion velocity and electron-transport speed of son, improve the electrical conduction efficiency of material.The too low then electric conductivity of multi-walled carbon nanotube content
Can be bad, the chemical property of lithium ion battery cannot be improved well；Conversely, when its too high levels, multi-walled carbon nanotube
It can be accumulated in lithium titanate nanometer sheet lamella, influence the crystallinity of composite material, " the zero of lithium titanate nanometer sheet cannot be given full play to
Compliance " also will affect the stability of composite structure, influence the cycle performance and service life of battery.It is sent out in the present invention
Bright people has found in an experiment, the mass ratio of lithium titanate nanometer sheet and multi-walled carbon nanotube is controlled at (3.5-6): more in 1 range
Wall carbon nano tube is dispersed in the lamella of lithium titanate nanometer sheet, and the nano lithium titanate composite material prepared has irregular
Flat crystal structure, and crystallinity is high, purity is high, stable structure.
The present invention also provides a kind of preparation methods of above-mentioned nano lithium titanate composite material, with titanium source, lithium source, conductive agent
Lithium titanate nanometer sheet is prepared for raw material, then using the lithium titanate nanometer sheet and the multi-walled carbon nanotube after acid oxidase as raw material
Prepare nano lithium titanate composite material.
Further, the preparation method of the nano lithium titanate composite material includes the following steps: step 1: lithium titanate is received
The preparation of rice piece: being (50-65) by titanium source, lithium source, conductive agent in mass ratio: (5-10): after 1 sampling, being added in ethyl alcohol,
Then plus water 22-26h is stirred under 350-450r/min mixing speed, continues to stir 0.5-1h；After the completion of stirring, gained is mixed
It closes object to be transferred in water heating kettle, keeps 35-38h in 170-200 DEG C of baking oven, obtain white powder；Then by the white powder
End is put into 75-90 DEG C of baking oven dry 5.5-7h afterwards three times with ethanol washing；It is transferred in atmosphere furnace after the completion of dry, in 700-
6-8h is calcined at 800 DEG C, lithium titanate nanometer sheet is made；Step 2: it the preparation of nano lithium titanate composite material: will be made in step 1
The lithium titanate nanometer sheet obtained is added to the water, and dispersion liquid A is made；After the effective acid oxidase of multi-wall carbon nano-tube, add water, dispersion liquid is made
B；Under 200-300r/min mixing speed, dispersion liquid A is added in dispersion liquid B, after mixing, decompression filters, and then exists
6-8h is kept the temperature in 200-230 DEG C of baking oven, nano lithium titanate composite material is made.
Lithium titanate white powder is prepared using hydro-thermal method, lithium titanate nanometer sheet is made after calcining, then respectively by titanium
Sour lithium nanometer sheet and the multi-walled carbon nanotube after acid oxidase are added to the water to form dispersion liquid A and dispersion liquid B, and dispersion liquid A is added
Enter in dispersion liquid B, is filtered after being uniformly mixed through decompression, keeps the temperature obtained nano lithium titanate composite material.
In lithium titanate nanometer sheet preparation process, conductive agent, which is added, can be improved the stability of lithium titanate nanometer sheet, while just
The electric conductivity of step enhancing lithium titanate nanometer sheet.In calcination process, the presence of conductive agent can enhance the steady of nanometer chip architecture
It is qualitative, make it at high temperature, crystalline structure, substance performance will not change, and be conducive to the crystallization for improving lithium titanate nanometer sheet
Degree, reduces the introducing of impurity and the generation of crystal defect, strengthens its " zero strain " characteristic.After multi-walled carbon nanotube is added, metatitanic acid
A miniature electric field is formed between lithium nanometer sheet lamella and multi-walled carbon nanotube, is promoted multi-walled carbon nanotube to be doped into lithium titanate and is received
In rice piece lamella, the binding force of multi-walled carbon nanotube and lithium titanate nanometer sheet lamella is improved, being conducive to, which enhances nano lithium titanate, answers
The stability of condensation material.
It is in the prior art usually to receive lithium titanate nanometer sheet with carbon modified in nano lithium titanate composite material preparation process
Rice material mixing, then calcines at high temperature, composite material is made.High-temperature calcination reaction is more violent, and process is not easy to control, forges
It is readily incorporated impurity when burning, crystal defect occurs, dispersion of the carbon nanomaterial in lithium titanate nanometer sheet is generated certain bad
Influence, then reduce composite material stability.
In the present invention, first multi-walled carbon nanotube is aoxidized using acid, after acid oxidase, the basic structure of multi-walled carbon nanotube
Essential change does not occur, i.e., will not reduce the performances such as conductive multi-walled carbon nanotube, thermally conductive, acid and alkali-resistance, high temperature resistant, will not reduce
Its mechanical property and processing performance.After acid oxidase, the active group of multi-wall carbon nano-tube pipe surface is dramatically increased, and is mainly shown as
Dispersibility and uniformity improve, and can effectively improve the binding force of multi-walled carbon nanotube Yu lithium titanate nanometer sheet, while making multi wall
Carbon nanotube is dispersed in the lamella of lithium titanate nanometer sheet.In composite material preparation process, by multi-walled carbon nanotube point
After evenly mixing, decompression filters for dispersion liquid and lithium titanate nanometer sheet dispersion liquid, then keeps the temperature at 200-230 DEG C, nano-titanium is made
Sour lithium composite material is avoided because high-temperature calcination, which leads to the introducing of impurity, reduces stability of material the problem of.
Further, the water heating kettle is the water heating kettle containing polytetrafluoroethyllining lining；The atmosphere furnace is air atmosphere
Furnace.Within 200 DEG C, the water heating kettle containing polytetrafluoroethyllining lining is able to satisfy reaction and requires water heating kettle reaction temperature, can protect
Card reaction is normally carried out, and the water heating kettle containing polytetrafluoroethyllining lining is common water heating kettle simultaneously, i.e. consersion unit is simply easy
?.Air atmosphere stove can meet calcining requirement of the invention, do not have to manufacture inert atmosphere, reduce production cost.Further
Ground, the titanium source are one or more of butyl titanate, iso-butyl titanate, metatitanic acid methyl esters, titanium tetrachloride.
Further, the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium chloride.
Further, the conductive agent is six trichloride hydrate gadoliniums.Rare-earth compound and its derivative are frequently as urging
Agent is applied in the synthesis of chemical products such as phosphate, is alternatively arranged as modifying agent applied to fields such as biological medicines, has and urge
Change the feature that activity is high, selectivity is good, dosage is few.Inventor attempts in the preparation process of lithium titanate nanometer sheet in the present invention
The production efficiency of lithium titanate nanometer sheet is improved using rare-earth compound, enhances the performance of lithium titanate nanometer sheet, simultaneously also
The preparation for wanting to promote nano lithium titanate composite material, improves the chemical property of nano lithium titanate composite material.Pass through
Preferably, inventor has found that gadolinium trichloride has both above-mentioned properties, by the addition of gadolinium trichloride, so that lithium titanate nanometer for experiment
The electric conductivity of piece increases, and further, the addition of gadolinium trichloride promotes multi-walled carbon nanotube in metatitanic acid well
Dispersion and combination in lithium nanometer sheet, make that multi-walled carbon nanotube is evenly dispersed in lithium titanate nanometer sheet lamella, is not easy to accumulate, no
Influence the crystal plane structure of lithium titanate nanometer sheet, and the composite material that forming properties are stable.Preferably, consider the source of raw material, use
Cost and Environmental Factors are measured, use six trichloride hydrate gadoliniums as conductive agent in the present invention, six trichloride hydrate gadoliniums can have
Effect improves the performance of lithium titanate nanometer sheet and nano lithium titanate composite material, and dosage is few, and cost is relatively low, environmentally friendly.
Further, the acid is at least one of nitric acid or sulfuric acid；The mass fraction of the acid is 60%-70%；Institute
The mass ratio for stating acid and the multi-walled carbon nanotube is (0.65-14.5): 1.Inventor has found in an experiment in the present invention, and acid is dense
Oxidation modification effect is best when degree is 60%-70%, the dispersibility of multi-walled carbon nanotube in water when acid concentration is too low, after oxidation
It is poor, it just will appear apparent depositional phenomenon in the short time (0.5h), with the increase of acid concentration, depositional phenomenon gradually weakens,
When acid concentration is 60%, after standing 3h, also there is not depositional phenomenon.When acid concentration is excessively high, multi-wall carbon nano-tube pipe surface meeting
There is deep oxidation, oxidation product is covered on multi-wall carbon nano-tube pipe surface, when with lithium titanate nanometer sheet compound tense, binding force compared with
Difference is unable to the stable nano lithium titanate composite material of forming properties.
The present invention also provides a kind of lithium ion battery, negative electrode material is above-mentioned nano lithium titanate composite material.
Lithium ion battery initial capacity is 140-185mAh/g in the present invention；Above-mentioned lithium ion battery energy with higher
Density tests discovery, above-mentioned lithium ion battery initial capacity under 1C electric current by the charge and discharge cycles under different current conditions
It can achieve 185 mAh/g, under the high currents such as 10C, 20C, 30C, corresponding initial capacity is respectively 155 mAh/g, 148
MAh/g and 143 mAh/g.
The invention has the following advantages that
1. the present invention adds conductive agent in lithium titanate nanometer sheet preparation process, is conducive to ion diffusion, more lithium ions are provided
It is embedded in site, improves multiplying power charging performance.Addition conductive agent can improve the stability of lithium titanate nanometer sheet, additionally it is possible to further increase
The binding ability of strong lithium titanate nanometer sheet and multi-walled carbon nanotube, raising lithium titanate nanometer sheet and nano lithium titanate composite material
Crystallinity and stability.
2. selecting the nitric acid of suitable concentration to carry out oxidation processes to multi-walled carbon nanotube in the present invention, can effectively improve
The dispersibility of multi-walled carbon nanotube improves the binding ability of multi-walled carbon nanotube and lithium titanate nanometer sheet, promotes multi-wall carbon nano-tube
Pipe is evenly dispersed in lithium titanate nanometer sheet lamella.
3. in the present invention in nano lithium titanate composite material preparation process, by multi-walled carbon nanotube dispersion liquid and lithium titanate
After evenly mixing, decompression filters nanometer sheet dispersion liquid, dry, and nano lithium titanate composite material is made, avoids because of high-temperature calcination
The problem of reducing stability of material because of the introducing of impurity.Complex method is simple and easy, is easy to control lithium titanate nanometer sheet and more
The ratio of wall carbon nano tube, component ratio that is easily controllable and grasping composite material.
4. nano lithium titanate composite material has preferably electrochemical reaction power, higher rate capability in the present invention,
And the features such as low electrochemical impedance.
Detailed description of the invention
Fig. 1 is the XRD spectrum of lithium titanate nanometer sheet and nano lithium titanate composite material in the present invention；
Fig. 2 is the SEM figure of lithium titanate nanometer sheet in the present invention；
Fig. 3 is the TEM figure of lithium titanate nanometer sheet in the present invention；
Fig. 4 is the SEM figure of nano lithium titanate composite material in the present invention；
Fig. 5 is the TEM figure of nano lithium titanate composite material in the present invention；
Fig. 6 is the HRTEM figure of nano lithium titanate composite material in the present invention；
Fig. 7 be lithium titanate nanometer sheet and nano lithium titanate composite material are prepared as negative electrode material using in the present invention respectively lithium from
Cycle performance figure of the sub- battery under different current densities；
Fig. 8 be lithium titanate nanometer sheet and nano lithium titanate composite material are prepared as negative electrode material using in the present invention respectively lithium from
Sub- battery recycles 500 weeks cycle performance figures under 10C current density；
Fig. 9 be lithium titanate nanometer sheet and nano lithium titanate composite material are prepared as negative electrode material using in the present invention respectively lithium from
The AC impedance figure of sub- battery, illustration is equivalent simulation circuit figure in figure；
In figure, LTO is lithium titanate nanometer sheet, and LTO/MWCNTs is nano lithium titanate composite material.
Specific embodiment
The present invention will be described in detail with reference to the accompanying drawings and examples.
1. the preparation of nano lithium titanate composite material.
Embodiment 1
Step 1: the preparation of lithium titanate nanometer sheet: 17mL butyl titanate, mono- hydronium(ion) lithia of 1.89g, 0.3g six are hydrated
Gadolinium trichloride is added in 20mL ethyl alcohol, after stirring for 24 hours under 400 r/min mixing speeds, 25mL water is added, continues to stir
0.5h；After the completion of stirring, gained mixture is transferred to 50mL and is contained in the water heating kettle of polytetrafluoroethyllining lining, in 180 DEG C of baking
36h is kept in case, obtains white powder, then the white powder is put into 80 DEG C of baking oven afterwards three times with ethanol washing and is done
Dry 6h；It is transferred in air atmosphere stove after the completion of dry, calcines 6h at 700 DEG C, lithium titanate nanometer sheet is made.
Step 2: the preparation of nano lithium titanate composite material: lithium titanate nanometer sheet 1g addition water obtained in step 1 is taken
In, dispersion liquid A is made；The nitric acid oxidation for being 65% by the effective 4.5g mass percent of 4.5g multi-wall carbon nano-tube, is then added
Dispersion liquid B is made in 100mL water, under 200r/min mixing speed, dispersion liquid A is added in dispersion liquid B, after mixing, is subtracted
Pressure filters, and then keeps the temperature 6h in 200 DEG C of baking oven, and nano lithium titanate composite material is made.
Lithium titanate nanometer sheet obtained and the XRD spectrum of nano lithium titanate composite material are as described in Fig. 1 in the present embodiment.
By attached drawing 1 it is found that referring to spinel lithium titanate standard card (JCPDS card No.49-0207), be made in the present embodiment
Lithium titanate nanometer sheet and nano lithium titanate composite material in the diffraction maximum that occurs and the diffraction maximum of pure lithium titanate correspond, i.e.,
The addition of multi-walled carbon nanotube does not influence the crystal plane structure of lithium titanate nanometer sheet in the present embodiment, can give full play to lithium titanate and receive
" zero strain " performance of rice piece；The intensity of diffraction maximum is high simultaneously, illustrates lithium titanate nanometer sheet and nanometer obtained in the present embodiment
Lithium titanate composite material crystal form is good, and crystallinity is high, purity is high, stable structure.
The SEM figure and TEM figure of lithium titanate nanometer sheet obtained are respectively as shown in attached drawing 2, attached drawing 3 in the present embodiment.This reality
The SEM figure, TEM figure, HRTEM for applying nano lithium titanate composite material obtained in example are schemed respectively such as attached drawing 4, attached drawing 5,6 institute of attached drawing
Show.It is compound in nano lithium titanate by attached drawing 3 it is found that lithium titanate nanometer sheet is irregular flat crystal structure in the present embodiment
In material, multi-walled carbon nanotube is dispersed in the lamella of lithium titanate nanometer sheet, has no effect on the crystal plane structure of lithium titanate nanometer sheet
(attached drawing 5, attached drawing 6).
Embodiment 2
Compared with Example 1, embodiment 2 the difference is that: in step 1, butyl titanate, a hydronium(ion) lithia, six
The dosage of trichloride hydrate gadolinium is respectively 13mL, 1.89g, 0.2g；In step 2, lithium titanate nanometer sheet, multi-walled carbon nanotube, nitre
The dosage of acid is respectively 4.5g, 1g, 4.5g, and wherein concentration of nitric acid is 55%(mass fraction).
Embodiment 3
Compared with Example 1, embodiment 3 the difference is that: in step 1, butyl titanate, a hydronium(ion) lithia, six
The dosage of trichloride hydrate gadolinium is respectively 15mL, 2.54g, 0.3g；In step 2, lithium titanate nanometer sheet, multi-walled carbon nanotube, nitre
The dosage of acid is respectively 4.5g, 1g, 4.5g, and wherein concentration of nitric acid is 75%(mass fraction).
Embodiment 4
Compared with Example 1, embodiment 4 the difference is that: in step 1, butyl titanate, a hydronium(ion) lithia, six
The dosage of trichloride hydrate gadolinium is respectively 16mL, 1.68g, 0.3g；In step 2, lithium titanate nanometer sheet, multi-walled carbon nanotube, nitre
The dosage of acid is respectively 4.2g, 1g, 2.2g, and wherein concentration of nitric acid is 65%(mass fraction).
Embodiment 5
Compared with Example 1, embodiment 5 the difference is that: in step 1, butyl titanate, a hydronium(ion) lithia, six
The dosage of trichloride hydrate gadolinium is respectively 12mL, 1.25g, 0.2g；In step 2, lithium titanate nanometer sheet, multi-walled carbon nanotube, nitre
The dosage of acid is respectively 5.5g, 1g, 2.2g, and wherein concentration of nitric acid is 65%(mass fraction).
Embodiment 6
Compared with Example 1, embodiment 6 the difference is that: in step 1, butyl titanate, a hydronium(ion) lithia, six
The dosage of trichloride hydrate gadolinium is respectively 15mL, 1.89g, 0.25g；In step 2, lithium titanate nanometer sheet, multi-walled carbon nanotube,
The dosage of nitric acid is respectively 5.8g, 1g, 8g, and wherein concentration of nitric acid is 65%(mass fraction).
Embodiment 7
Compared with Example 1, embodiment 7 the difference is that: in step 1, butyl titanate, a hydronium(ion) lithia, six
The dosage of trichloride hydrate gadolinium is respectively 14mL, 2.16g, 0.25g；In step 2, lithium titanate nanometer sheet, multi-walled carbon nanotube,
The dosage of nitric acid is respectively 6g, 1g, 8g, and wherein concentration of nitric acid is 65%(mass fraction).
Embodiment 8
Compared with Example 1, embodiment 7 the difference is that: in step 1, butyl titanate, a hydronium(ion) lithia, six
The dosage of trichloride hydrate gadolinium is respectively 18mL, 3.26g, 0.35g；In step 2, lithium titanate nanometer sheet, multi-walled carbon nanotube,
The dosage of nitric acid is respectively 3.5g, 1g, 8g, and wherein concentration of nitric acid is 65%(mass fraction).
Embodiment 9
Compared with Example 1, embodiment 9 the difference is that: in step 1, butyl titanate, a hydronium(ion) lithia, six
The dosage of trichloride hydrate gadolinium is respectively 21mL, 2.54g, 0.35g；In step 2, lithium titanate nanometer sheet, multi-walled carbon nanotube,
The dosage of nitric acid is respectively 4.5g, 1g, 10g, and wherein concentration of nitric acid is 65%(mass fraction).
Embodiment 10
Compared with Example 1, embodiment 10 the difference is that: in step 1, butyl titanate, a hydronium(ion) lithia,
The dosage of six trichloride hydrate gadoliniums is respectively 18mL, 2.85g, 0.3g；In step 2, lithium titanate nanometer sheet, multi-walled carbon nanotube,
The dosage of nitric acid is respectively 3.2g, 1g, 12g, and wherein concentration of nitric acid is 65%(mass fraction).
Butyl titanate, a hydronium(ion) lithia, the dosage of six trichloride hydrate gadoliniums are as shown in the table in embodiment 1-10:
Lithium titanate nanometer sheet, multi-walled carbon nanotube, the dosage of nitric acid are as shown in the table in embodiment 1-10:
2. the preparation of lithium ion battery.
By the lithium titanate nanometer sheet prepared in embodiment 1-10 and nano lithium titanate composite material respectively with Kynoar
(PVDF), acetylene black is that 80:10:10 is uniformly mixed according to mass ratio, carries out homogenate coating, is punched into circular electrode after dry
Piece is anode with metal lithium sheet, is assembled into CR2032 type button cell.
The test of cycle performance under different current density conditions is carried out respectively to the CR2032 type button cell being assembled into.
It is assembled respectively using the lithium titanate nanometer sheet and nano lithium titanate composite material that are prepared in embodiment 1 as raw material
The cycle performance test result of CR2032 type button cell is as shown in Fig. 7, by attached drawing 7 it is found that when current density is by 1C to 30C
It when variation, is recycled 10 weeks under each current density, the specific capacity of lithium ion battery is basically unchanged, and illustrates to assemble in the present embodiment
At lithium ion battery have good cyclical stability.But during electric discharge current density increases, with lithium titanate nanometer sheet
Manufactured battery is compared, and the specific capacity reduction speed of battery made of nano lithium titanate composite material is significant lower, illustrates nanometer
Lithium titanate composite material has more preferably cyclical stability in curent change, i.e. nano lithium titanate composite material is to electric current
What is changed is more adaptable, and is more suitable for wide curent change range.
It is assembled respectively using the lithium titanate nanometer sheet and nano lithium titanate composite material that are prepared in embodiment 1 as raw material
CR2032 type button cell recycles 500 weeks under 10C electric current respectively, and cycle performance result is as shown in Fig. 8, by attached drawing 8 it is found that
Under 10C electric current, two kinds of lithium ion batteries all have good cyclical stability, and capacity retention ratio is all larger than 75%.
It is assembled respectively using the lithium titanate nanometer sheet and nano lithium titanate composite material that are prepared in embodiment 1 as raw material
CR2032 type button cell carries out ac impedance measurement, and test result is as shown in Fig. 9, R in the illustration of attached drawing 9sFor ohm electricity
Resistance, RctFor charge transfer resistance, Zw is Warburg impedance, and CPE indicates electric double layer capacitance.By attached drawing 9 it is found that nano lithium titanate
Battery electrochemical impedance made of composite material is lower, and chemical property is more preferable.
Z-view software is utilized to the ac impedance measurement result for the battery that lithium titanate nanometer sheet in embodiment 1-10 assembles
Carry out digital simulation, gained Ohmic resistance Rs, charge transfer resistance RctThe result is as follows:
Utilize Z-view soft the ac impedance measurement result for the battery that nano lithium titanate composite material in embodiment 1-10 assembles
Part carries out digital simulation, gained Ohmic resistance Rs, charge transfer resistance RctThe result is as follows:
From the data in the table, battery charge transfer resistance made of nano lithium titanate composite material is significantly less than lithium titanate nanometer
Battery made of piece illustrates that the introducing of multi-walled carbon nanotube can reduce polarization, improves the diffuser efficiency of lithium ion, i.e. embodiment
Middle nano lithium titanate composite material has good chemical property.
Finally, it should be noted that above embodiments be only to illustrate the technical solution of the embodiment of the present invention rather than to its into
Row limitation, although the embodiment of the present invention is described in detail referring to preferred embodiment, those skilled in the art
It should be understood that the technical solution of the embodiment of the present invention can be still modified or replaced equivalently, and these are modified or wait
The range of modified technical solution disengaging technical solution of the embodiment of the present invention cannot also be made with replacement.
Claims (10)
1. a kind of nano lithium titanate composite material, it is characterised in that: it is made of lithium titanate nanometer sheet and multi-walled carbon nanotube, it is described
Multi-walled carbon nanotube is dispersed in the lamella of the lithium titanate nanometer sheet, and the lithium titanate nanometer sheet is received with the multi wall carbon
The mass ratio of mitron is (3.5-6): 1.
2. nano lithium titanate composite material as described in claim 1, it is characterised in that: the nano lithium titanate composite material is piece
Shape crystal structure.
3. a kind of preparation method of nano lithium titanate composite material, it is characterised in that: using titanium source, lithium source, conductive agent as raw material system
Then standby lithium titanate nanometer sheet prepares nanometer using the lithium titanate nanometer sheet and the multi-walled carbon nanotube after acid oxidase as raw material
Lithium titanate composite material.
4. the preparation method of nano lithium titanate composite material as claimed in claim 3, which comprises the steps of:
Step 1: the preparation of lithium titanate nanometer sheet: being (50-65) by titanium source, lithium source, conductive agent in mass ratio: (5-10): 1 takes
Then plus water it after sample, is added in ethyl alcohol, 22-26h is stirred under 350-450r/min mixing speed, continue to stir 0.5-1h；It stirs
After the completion of mixing, gained mixture is transferred in water heating kettle, 35-38h is kept in 170-200 DEG C of baking oven, obtains white powder；
Then dry 5.5-7h will be put into 75-90 DEG C of baking oven after white powder ethanol washing；Gas is transferred to after the completion of dry
In atmosphere furnace, 6-8h is calcined at 700-800 DEG C, lithium titanate nanometer sheet is made；
Step 2: the preparation of nano lithium titanate composite material: lithium titanate nanometer sheet obtained in step 1 is added to the water, and is made
Dispersion liquid A；After the effective acid oxidase of multi-wall carbon nano-tube, add water, dispersion liquid B is made；It, will under 200-300r/min mixing speed
Dispersion liquid A is added in dispersion liquid B, and after mixing, decompression filters, and then keeps the temperature 6-8h in 200-230 DEG C of baking oven, is made
Nano lithium titanate composite material.
5. the preparation method of nano lithium titanate composite material as claimed in claim 4, it is characterised in that: the water heating kettle be containing
The water heating kettle of polytetrafluoroethyllining lining；The atmosphere furnace is air atmosphere stove.
6. the preparation method of nano lithium titanate composite material as claimed in claim 3, it is characterised in that: the titanium source is metatitanic acid four
One or more of butyl ester, iso-butyl titanate, metatitanic acid methyl esters, titanium tetrachloride.
7. the preparation method of nano lithium titanate composite material as claimed in claim 3, it is characterised in that: the lithium source is hydroxide
One or more of lithium, lithium carbonate, lithium nitrate, lithium chloride.
8. the preparation method of nano lithium titanate composite material as claimed in claim 3, it is characterised in that: the conductive agent is six water
Close gadolinium trichloride.
9. the preparation method of nano lithium titanate composite material as claimed in claim 3, it is characterised in that: the acid is nitric acid or sulphur
At least one of acid；The mass fraction of the acid is 60%-70%；The acid and the mass ratio of the multi-walled carbon nanotube are
(0.65-14.5): 1.
10. a kind of lithium ion battery, it is characterised in that: the negative electrode material of the lithium ion battery is as claim 1-2 is any
The nano lithium titanate composite material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734123A (en) * | 2018-12-28 | 2019-05-10 | 南通奥新电子科技有限公司 | A kind of preparation method and applications of nano lithium titanate |
| CN110759379A (en) * | 2019-10-31 | 2020-02-07 | 湘潭大学 | Preparation method and application of 0D/2D heterostructure composite negative electrode material |
| CN110828815A (en) * | 2019-11-13 | 2020-02-21 | 河北彩客化学股份有限公司 | Lithium battery negative electrode material and preparation method thereof |
| CN115799486A (en) * | 2023-02-03 | 2023-03-14 | 中国华能集团清洁能源技术研究院有限公司 | Micron-sized lithium titanate and multi-walled carbon nanotube composite material and preparation method and application thereof |
-
2018
- 2018-07-27 CN CN201810845322.4A patent/CN109037632A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734123A (en) * | 2018-12-28 | 2019-05-10 | 南通奥新电子科技有限公司 | A kind of preparation method and applications of nano lithium titanate |
| CN110759379A (en) * | 2019-10-31 | 2020-02-07 | 湘潭大学 | Preparation method and application of 0D/2D heterostructure composite negative electrode material |
| CN110828815A (en) * | 2019-11-13 | 2020-02-21 | 河北彩客化学股份有限公司 | Lithium battery negative electrode material and preparation method thereof |
| CN115799486A (en) * | 2023-02-03 | 2023-03-14 | 中国华能集团清洁能源技术研究院有限公司 | Micron-sized lithium titanate and multi-walled carbon nanotube composite material and preparation method and application thereof |
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