CN108232175A - A kind of lithium ion battery graphite/lithium titanate composite anode material and preparation method - Google Patents
A kind of lithium ion battery graphite/lithium titanate composite anode material and preparation method Download PDFInfo
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- CN108232175A CN108232175A CN201810117708.3A CN201810117708A CN108232175A CN 108232175 A CN108232175 A CN 108232175A CN 201810117708 A CN201810117708 A CN 201810117708A CN 108232175 A CN108232175 A CN 108232175A
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- graphite
- lithium titanate
- lithium
- anode material
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 85
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 84
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000010439 graphite Substances 0.000 title claims abstract description 79
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000010405 anode material Substances 0.000 title claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 71
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- 238000005336 cracking Methods 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 7
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000203 mixture Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002635 aromatic organic solvent Substances 0.000 claims description 3
- -1 feature It is Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
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- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- 239000002344 surface layer Substances 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
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- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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Classifications
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- 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
- H01M4/366—Composites as layered products
-
- 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)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of lithium ion battery graphite/lithium titanate composite anode materials and preparation method, graphite/the lithium titanate anode material is to form lithium titanate and organic cracking carbon coating layer in graphite type material particle surface, is formed using graphite type material as kernel, using composite material of the lithium titanate with organic cracking carbon coating layer as shell mechanism；Preparation method includes the following steps：(1) by graphite type material, lithium titanate, organic cracking carbon carbon source according to 100：1‑10：15 mass ratio is added in into inorganic solvent or organic solvent, is mixed, dry；(2) gained composite material is warming up to 600 1050 DEG C with the rate of 1 20 DEG C/min and is sintered under atmosphere of inert gases protection, and keep the temperature 1 10h to get；Graphite/lithium titanate composite anode material in the present invention can effectively improve safety, high rate performance, cycle performance and the high temperature performance of graphite negative electrodes material, while preparation method is simple for process controllable, of low cost, is easy to mass industrial production.
Description
Technical field
The present invention relates to lithium ion battery negative material fields, and in particular to a kind of lithium ion battery graphite/lithium titanate
Composite negative pole material and preparation method.
Background technology
Carbonaceous material because with relatively low intercalation potential, good cycle performance, relative moderate price, environmental-friendly etc.
Advantage is widely used in lithium ion battery negative material.Wherein, graphite type material because in reversible discharge specific capacity, filling for the first time
The outstanding advantage of discharging efficiency, voltage platform, manufacture cost etc. is the negative material category of current mainstream, in future one
Also will be the important candidate of lithium ion battery negative material in the section time.But the relatively low intercalation potential of graphite type material, easily with
The characteristics of electrolyte forms SEI films on surface so that it is short of in terms of safety and high rate performance.It is it is then desired to right
Graphite type material is modified processing to improve its chemical property.
Lithium titanate material has higher discharge platform, higher ionic diffusion coefficient, extremely low volume expansion, overlength
Cycle life, good low temperature charge-discharge performance so that there is higher peace using its lithium ion battery as negative material
Quan Xing, again forthright and wider temperature in use section, thus occupy a tiny space in lithium ion battery negative material.But
The relatively low theoretical specific capacity of lithium titanate material (~175mAh/g) and higher intercalation potential (~1.5V) lead to its energy density
It is relatively low, significantly limit its application field.Graphite type material is modified using lithium titanate material, has both it good
Safety and high rate performance are a kind of good modified approach.
At present, the existing report being modified using lithium titanate material to graphite type material.Application number
The domestic patent of invention of 201210124713.X discloses a kind of composite cathode material of silicon/carbon/graphite and its system of lithium titanate coating modification
Preparation Method and application；The domestic patent of invention of application number 201410344991.5 discloses a kind of lithium titanate cladding surface treated
Negative material, preparation method and the application of graphite, the negative material is in surface treated graphite-like basis negative material particle surface
Upper formation lithium titanate clad, graphite negative electrodes material to be overcome to analyse the safety problems such as lithium in applying, overcomes existing graphite
Class negative material uses unmatched defect with battery system under excessive temperature or too low temperature, improves existing modification or modification
Lithium titanate particle caused by method is reunited, graphite particle surface coats the problems such as uneven because anisotropy causes；Application No. is
201710178160.9 domestic patent of invention disclose a kind of preparation method of lithium titanate composite cathode material of silicon/carbon/graphite, pass through machine
Tool mixing, crushes the three-dimensional conductive network that lithium titanate is distributed in graphite composition by the means such as nodularization, high temperature sintering at isostatic pressed fusion
In.However, first two method all employs preparation and and the graphite that more complicated sol gel process carries out lithium titanate material
Class material it is compound, it is difficult to realize lithium titanate material in the uniform cladding on graphite material surface and grasped in industrialized mass production
It is larger to make difficulty, is unfavorable for mass producing；Lithium titanate material is then placed in the inside of composite structure, nothing by later approach
It is effectively modified that method makes full use of the characteristic of lithium titanate to carry out graphite material.
Invention content
For it is existing the technical issues of, the present invention proposes a kind of lithium ion battery graphite/lithium titanate composite negative pole material
Material and preparation method, the graphite/lithium titanate composite anode material can effectively improve the safety of graphite negative electrodes material, multiplying power
Performance, cycle performance and high temperature performance, while preparation method is simple for process controllable, of low cost, is easy to batch chemical industry life
Production.
In order to achieve the above object, the present invention is achieved by the following technical programs：
A kind of lithium ion battery graphite/lithium titanate composite anode material, the graphite/lithium titanate anode material are in stone
Black class material granule surface forms lithium titanate and organic cracking carbon coating layer, is formed using graphite type material as kernel, with lithium titanate
With graphite/lithium titanate composite material that organic cracking carbon coating layer is shell mechanism；
The raw material for being used to prepare the graphite/lithium titanate composite anode material includes graphite type material, lithium titanate, organic splits
Solve carbon carbon source；The graphite type material, lithium titanate, organic cracking carbon carbon source mass ratio be 100：1-10：1-5.
Preferably, the graphite type material is one kind in native graphite, Delanium, carbonaceous mesophase spherules and soft charcoal
Or at least two mixture, grain size be 5-30 μm, purity >=99%.
Preferably, the grain size of the lithium titanate be 10-500nm, purity >=99.0%.
Preferably, organic cracking carbon carbon source is glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone, polypropylene
The mixture of one or more of acid, polyacrylonitrile, epoxy resin, phenolic resin, pitch.
A kind of lithium ion battery preparation method of graphite/lithium titanate composite anode material, includes the following steps：
(1) by graphite type material, lithium titanate, organic cracking carbon carbon source according to 100：1-10：The mass ratio of 1-5 is added in nothing
In solvent or organic solvent, and mixed using homogenizer, be then dried, obtain graphite/carbon source clad/
Lithium titanate composite material；
(2) composite material obtained by step (1) is heated up under atmosphere of inert gases protection with the rate of 1-20 DEG C/min
It is sintered to 600-1050 DEG C, and keeps the temperature 1-10h to get graphite/lithium titanate composite anode material.
Preferably, the inorganic solvent is water, and organic solvent is alcohol organic solvent, ether organic solvent, ketone have
The mixture of one or more of solvent, aromatic organic solvent.
Preferably, the alcohol organic solvent be methanol, ethyl alcohol, ethylene glycol, normal propyl alcohol, isopropanol, propylene glycol, the third three
It is one or more in alcohol, n-butanol, isobutanol；Ether organic solvent is ether, positive propyl ether, one kind in n-butyl ether or more
Kind；Organic solvent of ketone is acetone, one or more in butanone, pentanone；Aromatic organic solvent is benzene, toluene, diformazan
It is one or more in benzene, ethylo benzene.
Preferably, the inert gas is the mixed gas of one or more of nitrogen, argon gas, helium.
The beneficial effects of the invention are as follows：
(1) present invention by lithium titanate particle tight bond on the cracking carbon-coating of graphite core surface, it is not easily to fall off, formed
Firm clad advantageously reduces contact area, increase lithium titanate material and the electrolysis at graphite material interface and electrolyte
The contact area of liquid so as to reduce the generation thickness of SEI films, enhancing lithium ion diffusion rate, improves the peace of graphite cathode material
Quan Xing, high rate performance, cycle performance.
(2) present invention using industrially obtain it is widely used be dispersed with stirring, dry, the conventional means such as high temperature sintering,
Preparing has using graphite type material as the graphite/lithium titanate Compound Negative of kernel, lithium titanate and carbon material clad for shell mechanism
Pole material, the preparation method is simple for process controllable, of low cost, is easy to mass industrial production.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is the structure diagram of graphite/lithium titanate composite anode material of embodiment 1；
Fig. 2 is the scanning electron microscope sem figure of graphite/lithium titanate composite anode material of embodiment 1.
Specific embodiment
Purpose, technical scheme and advantage to make the embodiment of the present invention are clearer, below in conjunction with the embodiment of the present invention,
Technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
All other embodiments obtained under the premise of creative work, shall fall within the protection scope of the present invention.
Embodiment 1：
A kind of lithium ion battery preparation method of graphite/lithium titanate composite anode material, includes the following steps：
(1) by native graphite powder material (grain size is 20 μm, and purity is 99.5%), lithium titanate powdery material (grain size
For 100nm, purity 99.5%), polyethylene glycol material is according to 100：10：5 mass ratio is added in into water, and uses high-speed stirring
The machine of mixing is mixed, and is then spray-dried, and obtains graphite/organic carbon source clad/lithium titanate composite material；
(2) by the composite material obtained by step (1) in the case where nitrogen protective atmosphere encloses protection, with 5 DEG C/min speed in high temperature furnace
Rate is warming up to 850 DEG C and is sintered, and keeps the temperature 4h to get graphite/lithium titanate composite anode material.
Embodiment 2：
A kind of lithium ion battery preparation method of graphite/lithium titanate composite anode material, includes the following steps：
(1) by native graphite powder material (grain size be 25 μm, purity 99.0%), lithium titanate powdery material, (grain size is
200nm, purity 99.5%), polyethylene glycol material is according to 100：5：5 mass ratio is added in into water, and uses high-speed stirred
Machine is mixed, and is then spray-dried, and obtains graphite/organic carbon source clad/lithium titanate composite material；
(2) by the composite material obtained by step (1) in the case where nitrogen protective atmosphere encloses, with 10 DEG C/min rate liters in high temperature furnace
Temperature is sintered, and keep the temperature 2h to get graphite/lithium titanate composite anode material to 900 DEG C.
Embodiment 3：
A kind of lithium ion battery preparation method of graphite/lithium titanate composite anode material, includes the following steps：
(1) by native graphite powder material (grain size be 30 μm, purity 99.5%), lithium titanate powdery material, (grain size is
400nm, purity 99.5%), polyacrylic acid material is according to 100：1：2 mass ratio is added in into ethyl alcohol, and uses high-speed stirring
The machine of mixing is mixed, and is then spray-dried, and obtains graphite/organic carbon source clad/lithium titanate composite material；
(2) by the composite material obtained by step (1) in the case where argon gas protects atmosphere, with 15 DEG C/min rate liters in high temperature furnace
Temperature is sintered, and keep the temperature 1h to get graphite/lithium titanate composite anode material to 700 DEG C.
Embodiment 4：
A kind of lithium ion battery preparation method of graphite/lithium titanate composite anode material, includes the following steps：
(1) by carbonaceous mesophase spherules (grain size be 10 μm, purity 99.5%), lithium titanate powdery material (grain size 50nm,
Purity be 99.5%), phenolic resin material is according to 100：3：1 mass ratio is added in into acetone, and using homogenizer into
Row mixing, is then spray-dried, obtains graphite/organic carbon source clad/lithium titanate composite material；
(2) by the composite material obtained by step (1) in the case where argon gas protects atmosphere, with 20 DEG C/min rate liters in high temperature furnace
Temperature is sintered, and protect 7h to get graphite/lithium titanate composite anode material to 1050 DEG C.
Embodiment 5：
In the present embodiment, by the native graphite powder material in step (1) in embodiment 1 replace with grain size for 20 μm, it is pure
The Delanium powder material for 99.5% is spent, other preparation processes remain unchanged.
Embodiment 6：
In the present embodiment, the polyethylene glycol material in step (1) in embodiment 1 is replaced with into polyvinylpyrrolidone material
Material, other preparation processes remain unchanged.
Comparative example 1：
Use the native graphite powder material as a comparison case 1 that grain size is 99.5% for 20 μm, purity.
Comparative example 2：
Use the lithium titanate powdery material as a comparison case 2 that grain size is 99.5% for 100nm, purity.
Performance test：
By the powder in graphite/lithium titanate composite anode material in 1-6 of the embodiment of the present invention and comparative example 1, comparative example 2
Material is tested for the property, and test result is as shown in table 1.
Table 1：
Graphite obtained through the embodiment of the present invention/lithium titanate composite negative pole material it can be seen from more than test result
Compared with comparative example, high rate performance and cycle performance are largely increased material.Reason can be attributed to lithium titanate material particle because
Tight bond is not easily to fall off on the cracking carbon-coating of graphite surface, forms firm lithium titanate clad, reduces graphite
The contact area of material interface and electrolyte reduces the generation thickness of SEI films and enhances lithium ion diffusion rate, so as to improve
The high rate performance and cycle performance of composite material.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those of ordinary skill in the art that：It still can be to aforementioned each implementation
Technical solution recorded in example modifies or carries out equivalent replacement to which part technical characteristic；And these modification or
It replaces, the spirit and scope for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution.
Claims (8)
1. a kind of lithium ion battery graphite/lithium titanate composite anode material, it is characterised in that：
Graphite/the lithium titanate anode material is to form lithium titanate and organic cracking carbon coating in graphite type material particle surface
Layer forms using graphite type material as kernel, is multiple as graphite/lithium titanate of shell mechanism with organic cracking carbon coating layer using lithium titanate
Condensation material；
The raw material for being used to prepare the graphite/lithium titanate composite anode material includes graphite type material, lithium titanate, organic cracking carbon
Carbon source；The graphite type material, lithium titanate, organic cracking carbon carbon source mass ratio be 100：1-10：1-5.
2. lithium ion battery according to claim 1 graphite/lithium titanate composite anode material, which is characterized in that described
Graphite type material be one kind or at least two mixture in native graphite, Delanium, carbonaceous mesophase spherules and soft charcoal,
Its grain size is 5-30 μm, purity >=99%.
3. lithium ion battery according to claim 1 graphite/lithium titanate composite anode material, which is characterized in that described
Lithium titanate grain size for 10-500nm, purity >=99.0%.
4. lithium ion battery according to claim 1 graphite/lithium titanate composite anode material, which is characterized in that described
Organic cracking carbon carbon source is glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, polyacrylonitrile, asphalt mixtures modified by epoxy resin
The mixture of one or more of fat, phenolic resin, pitch.
5. a kind of lithium ion battery preparation method of graphite/lithium titanate composite anode material, which is characterized in that including following step
Suddenly：
(1) by graphite type material, lithium titanate, organic cracking carbon carbon source according to 100：1-10：The mass ratio of 1-5 is added in inorganic molten
It in agent or organic solvent, and is mixed using homogenizer, is then dried, obtain graphite/carbon source clad/metatitanic acid
Lithium composite material；
(2) composite material obtained by step (1) is warming up under atmosphere of inert gases protection with the rate of 1-20 DEG C/min
600-1050 DEG C is sintered, and keeps the temperature 1-10h to get graphite/lithium titanate composite anode material.
6. the lithium ion battery according to claim 5 preparation method of graphite/lithium titanate composite anode material, feature
It is, the inorganic solvent is water, and organic solvent is alcohol organic solvent, ether organic solvent, organic solvent of ketone, fragrance
The mixture of one or more of same clan's organic solvent.
7. the lithium ion battery according to claim 6 preparation method of graphite/lithium titanate composite anode material, feature
Be, the alcohol organic solvent for methanol, ethyl alcohol, ethylene glycol, normal propyl alcohol, isopropanol, propylene glycol, glycerine, n-butanol,
It is one or more in isobutanol；Ether organic solvent is ether, one or more in positive propyl ether, n-butyl ether；Ketone is organic
Solvent is acetone, one or more in butanone, pentanone；Aromatic organic solvent is benzene,toluene,xylene, in ethylo benzene
It is one or more.
8. the lithium ion battery according to claim 5 preparation method of graphite/lithium titanate composite anode material, feature
It is, the inert gas is the mixed gas of one or more of nitrogen, argon gas, helium.
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