CN102569769A - Preparation method for lithium titanate and graphene composite electrode materials - Google Patents
Preparation method for lithium titanate and graphene composite electrode materials Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007772 electrode material Substances 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- -1 titanium ions Chemical class 0.000 claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000002135 nanosheet Substances 0.000 claims abstract description 6
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 5
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000013066 combination product Substances 0.000 claims description 7
- 229940127555 combination product Drugs 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000000087 stabilizing effect Effects 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- ZUILKEWVWUKSAO-ZZXKWVIFSA-N 4-coumaroyltriacetic acid lactone Chemical compound C1=CC(O)=CC=C1\C=C\C(=O)CC1=CC(O)=CC(=O)O1 ZUILKEWVWUKSAO-ZZXKWVIFSA-N 0.000 claims description 4
- QMXOFBXZEKTJIK-UHFFFAOYSA-N Glycinol Natural products C1=C(O)C=C2OCC3(O)C4=CC=C(O)C=C4OC3C2=C1 QMXOFBXZEKTJIK-UHFFFAOYSA-N 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 239000010936 titanium Substances 0.000 abstract description 15
- 238000002604 ultrasonography Methods 0.000 abstract description 7
- 239000007767 bonding agent Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 230000005669 field effect Effects 0.000 description 6
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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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- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A preparation method for lithium titanate and graphene composite electrode materials comprises the following steps: solution A containing lithium ion is prepared by dissolving surface-active agent, template agent and lithium compound into deionized water; titanium compound is added into graphene solution with the concentration of 0.1 to 0.5 g/l, and solution B containing titanium ions is prepared through ultrasound and stirring; under the effect of ultrasonic wave field, the solution A is added into the solution B, then bonding agent is added, and solution C is prepared; the solution C is moved into a polytetrafluoroethylene reaction kettle, and reaction is performed under 140 to 200 DEG C; then leaching, washing and drying to the solution are performed, and eventually, composite products are produced under the atmosphere of argon gas. The lithium titanate in the composite product is nanosheet lithium titanate, can be fully mixed and contacted with the sheet graphene, and the electric conductance and ion electric conductance of the lithium titanate material are improved greatly; and the composite product is classified as electrode material with excellent and high rate charge-discharge performance.
Description
Technical field
The present invention relates to a kind of lithium titanate
WithThe preparation method of graphene composite material, the preparation method and the combination electrode material of the electrode material that especially a kind of sheet lithium titanate and Graphene are compound.
Background technology
The energy and environment problem is serious day by day, and the exploitation of clean energy resource is extremely urgent with use, and the development electric motor car is the inexorable trend of future development.The large-scale application of green energy resources such as wind energy, solar energy, geothermal energy is had higher requirement to energy storage device, particularly to useful life of energy-storage battery.
Various electronic equipments and electric automobile, hybrid vehicle fast development have proposed harsh more requirement, particularly its power-performance to the lithium ion battery that energy is provided for it.Present widely used carbon negative pole material makes that the battery system fail safe is relatively poor because hypopotenia is easy to electrolyte and reacts; In addition, the carbon negative pole material power-performance is relatively poor, can not solve its fast charging and discharging problem, therefore can not satisfy the instructions for use of electric motor car.
The major obstacle that lithium-ion-power cell is applied to electric automobile is fail safe, energy density, power density and the high power charge-discharge performance of battery, and the key factor that restricts above-mentioned performance is the employed electrode material of battery.The lithium-ion-power cell of being studied at present is a positive electrode with LiFePO4, nickel-cobalt-manganese ternary material, LiMn2O4 usually; Material with carbon element is a negative material; Though the security performance of above-mentioned three kinds of positive electrodes itself is better, embedding lithium carbon negative pole material when the battery abnormal condition is used can with electrolyte generation vigorous reaction, emit a large amount of heat and imflammable gas; Cause battery failure, even blast.Use material with carbon element never effectively to be solved as the safety issue of the large-capacity high-power type lithium-ion-power cell of negative pole; Seriously restricted its application on electric automobile; So how to solve the fundamental issue that the safety issue of lithium-ion-power cell has become its industrialized development of puzzlement, also be the key issue that hinders electric vehicle industrialization.
Solving the security of lithium-ion-power cell key of problem is with safer, littler with the electrolyte reactivity alternative carbon negative pole material of negative material.Lithium titanate (Li
4Ti
5O
12) have lot of advantages as a kind of novel negative material; For example security performance is good, long service life, efficiency for charge-discharge height, Stability Analysis of Structures etc.; Potentially be used widely, be considered to lithium ion battery negative material of future generation the most likely in the lithium-ion-power cell field.And the present subject matter that faces of lithium titanate is that the intrinsic electronic conductance is low, and conductivity is relatively poor, has restricted it as the application of high power negative material in power-type lithium ion battery.The main path that improves the high-rate charge-discharge capability of lithium titanate at present has following three kinds:
Preparation nanometer particle size Li
4Ti
5O
12, mainly, can obtain nanoscale, the uniform Li of Dispersion of Particles through the sol-gel process preparation
4Ti
5O
12Particle, complex process, cost is higher, is unfavorable for industrialization;
The Li for preparing porous or hollow structure with template
4Ti
5O
12, can effectively improve the electric conductivity and the high-rate charge-discharge capability of material;
Coat raising Li through doped with metal elements and carbon
4Ti
5O
12The power-performance of electrode material is present the most frequently used method.
Present preparation of industrialization Li
4Ti
5O
12The main method that adopts is a high temperature solid-state method, and synthetic method is with TiO
2(be mainly Li with the lithium source
2CO
3, LiOH and LiNO
3) fully mix, high temperature sintering obtains product.Though solid-phase synthesis technology is simple, cost is low, most of products are micron orders, and distribution of particles is uneven, and high rate capability is poor.
At present, improve Li
4Ti
5O
12The method of high rate performance also has Li
4Ti
5O
12Mutually compound with material with carbon elements such as Graphene, CNT, carbon nanocoils, these methods can improve its high rate performance well, but because Li wherein
4Ti
5O
12All be to exist, can't fully contact with peacekeeping two-dimensional material such as CNT, Graphenes that contact area is limited, limited the further raising of its performance at compound tense with the three dimensional particles shape.
Summary of the invention
The present invention aims to provide the synthetic method and the combination electrode material of a kind of lithium titanate and graphene combination electrode material, and used Graphene is the Graphene that this laboratory oneself preparation or market are bought, the Li that this method is synthetic
4Ti
5O
12Be the nano-sheet structure, can contact more fully, characteristics such as high as the power battery cathode material specific capacity, that high-rate charge-discharge capability is good, efficiency for charge-discharge is high, good cycle, fail safe are good with the Graphene that is all laminated structure.
Lithium titanate of the present invention and graphene combination electrode material preparation method's detailed content is following:
(1), the mol ratio according to surfactant and lithium ion is 0.1 ~ 1:1; The mol ratio of template and lithium ion is 0.05 ~ 0.5:1; The surfactant, template and the lithium compound that take by weighing respective quality are dissolved in the deionized water under stirring condition; Stir 0.5 ~ 5h, make and contain the stabilizing solution A that lithium concentration is 0.1 ~ 5mol/L;
(2), under the ultrasonic wave condition; According to the mass ratio of Graphene in the end-product and lithium titanate is 1 ~ 30: 100 ratio, in concentration is the Graphene solution of 0.1 ~ 0.5g/L, adds titanium compound, ultrasonic 15 ~ 30min; Stir 1 ~ 3h, make the solution B that titaniferous concentration is 0.1 ~ 5mol/L;
(3), under the ultrasound field effect, solution A is joined in the solution B, stir 5 ~ 60min, adding with product lithium titanate mol ratio is 0.05 ~ 0.5: 1 adhesive again, obtains solution C;
(4), the gained solution C is moved in the polytetrafluoroethylene agitated reactor, put into baking oven, at 140 ~ 200 ℃ of reaction 12 ~ 72h down;
(5), gained solution is carried out suction filtration, washing, drying, at last under argon gas atmosphere in 500 ~ 800 ℃ of sintering 2 ~ 24h, obtain end-product after the cooling.
Wherein, the preferred softex kw of employed surfactant (CTAB), or hexadecyltrimethylammonium chloride (CTAL), or lauryl sodium sulfate, perhaps two or more combination arbitrarily between them.
Preferred urea (the CON of employed template
2H
4), or block polymer P123, or ethylenediamine, perhaps two or more combination arbitrarily between them.
The preferred lithium hydroxide of employed lithium compound, or lithium carbonate, or lithia, or lithium acetate, or lithium oxalate, or lithium chloride perhaps adopt in them the mixture of two or more compositions arbitrarily.
Described titanium compound is selected at least a in butyl titanate, titanyl sulfate, titanium tetrachloride, Titanium Nitrate, tetraethyl titanate, tetraisopropyl titanate and the metatitanic acid methyl esters for use.
Described binding agent is selected at least a among hydrazine hydrate, glycinol and the N methyl pyrrolidone three for use.
Adopt the lithium titanate and the graphene combination electrode material of method for preparing, it is characterized in that: the lithium titanate in this combination electrode material is the nano-sheet lithium titanate, and the mass ratio of Graphene and lithium titanate is 1 ~ 30: 100.
Lithium titanate that preparation method of the present invention synthesized and graphene combination electrode material make full use of with the compact characteristics of dimension structural material, utilize prepared nano-sheet lithium titanate, fully mix contacting with the Graphene that is all sheet, have greatly improved Li simultaneously
4Ti
5O
12The electronic conductance of material and ionic conductance make it become the electrode material with very good high-rate charge-discharge capability.
This method has the advantages that synthesis technique is simple, cost is low, and the preparation process is controlled easily.
Description of drawings
The Li of Fig. 1 for making among embodiment 1 and the embodiment 2
4Ti
5O
12X-ray diffracting spectrum;
The Li that Fig. 2 makes for embodiment 1
4Ti
5O
12Shape appearance figure;
The shape appearance figure of the lithium titanate that Fig. 3 makes for embodiment 2/Graphene combination product;
The Li that Fig. 4 makes for embodiment 1 and embodiment 2
4Ti
5O
12The rate charge-discharge performance curve.
Embodiment
(1), weighing 2.00g softex kw (CTAB), 0.32g urea (CON
2H
4) and 0.96g lithium hydroxide (LiOH.H
2O) be dissolved in the 60ml deionized water, stir 1h, make and contain the stabilizing solution A that lithium concentration is about 0.4mol/L.
(2), under the state of sonicated, in the 30ml deionized water, add the 4.08ml butyl titanate, ultrasonic 15min stirs 1h, makes to contain the solution B that titanium ion concentration is 0.4mol/L.
(3), under the ultrasound field effect, solution A is joined in the solution B, stir 5 min, add the 5ml hydrazine hydrate again, obtain solution C.
(4), the gained solution C is moved in the polytetrafluoroethylene agitated reactor, put into baking oven, at 180 ℃ of reaction 48h down.
(5), gained solution is carried out suction filtration, washing, drying, at last under argon gas atmosphere in 600 ℃ of sintering 6h, obtain the lithium titanate product after the cooling, its shape appearance figure is seen Fig. 2.
Gained sheet lithium titanate and metal lithium sheet are done the performance that electrode is formed battery and test battery.With reference to Fig. 4, the 10C charging and discharging capacity surpasses 110mAh/g, and the 50C charging and discharging capacity reaches 90 mAh/g, and the 100C charging and discharging capacity reaches 75mAh/g.
(1), weighing 2,00g softex kw (CTAB), 0.32g urea (CON
2H
4) and 0.96g lithium hydroxide (LiOH.H
2O) be dissolved in the 60ml deionized water, stir 1h, make and contain the stabilizing solution A that lithium concentration is about 0.4mol/L.
(2), under the state of sonicated, in the 23ml deionized water, adding 7ml concentration is the Graphene solution of 0.3g/L, adds the 4.08ml butyl titanate then, ultrasonic 15min stirs 1h, makes to contain the solution B that titanium ion concentration is 0.4mol/L.
(3), under the ultrasound field effect, solution A is joined in the solution B, stir 5 min, add the 5ml hydrazine hydrate again, obtain solution C.
(4), the gained solution C is moved in the polytetrafluoroethylene agitated reactor, put into baking oven, at 180 ℃ of reaction 48h down.
(5), gained solution is carried out suction filtration, washing, drying, at last under argon gas atmosphere in 600 ℃ of sintering 6h, obtain the combination product of lithium titanate and Graphene after the cooling, its shape appearance figure is seen Fig. 3.
Gained sheet lithium titanate/graphene composite material and metal lithium sheet are done the performance that electrode is formed battery and test battery.With reference to Fig. 4, the reversible charging and discharging capacity of 10C surpasses 125mAh/g, and the 50C charging and discharging capacity reaches 100 mAh/g, and the 100C charging and discharging capacity reaches 80mAh/g.
Embodiment 3
(1), weighing 2,00g softex kw (CTAB), 0.32g urea (CON
2H
4) and 0.96g lithium hydroxide (LiOH.H
2O) be dissolved in the 60ml deionized water, stir 1h, make and contain the stabilizing solution A that lithium concentration is about 0.4mol/L.
(2), under the state of sonicated, in the 17ml deionized water, adding 13ml concentration is the Graphene solution of 0.3g/L, adds the 4.08ml butyl titanate then, ultrasonic 15min stirs 1h, makes to contain the solution B that titanium ion concentration is 0.4mol/L.
(3), under the ultrasound field effect, solution A is joined in the solution B, stir 5 min, add the 5ml hydrazine hydrate again, obtain solution C.
(4), the gained solution C is moved in the polytetrafluoroethylene agitated reactor, put into baking oven, at 180 ℃ of reaction 48h down.
(5), gained solution is carried out suction filtration, washing, drying, at last under argon gas atmosphere in 600 ℃ of sintering 6h, obtain the combination product of lithium titanate and Graphene after the cooling.
Embodiment 4
(1), weighing 3,00g hexadecyltrimethylammonium chloride (CTAL), 0.32g urea (CON
2H
4) and 0.96g lithium hydroxide (LiOH.H
2O) be dissolved in the 60ml deionized water, stir 1h, make and contain the stabilizing solution A that lithium concentration is about 0.4mol/L.
(2), under the state of sonicated, in the 30ml deionized water, adding 4ml concentration is the Graphene solution of 0.3g/L, and then adds the 4.08ml butyl titanate, ultrasonic 15min stirs 1h, makes to contain the solution B that titanium ion concentration is 0.4mol/L.
(3), under the ultrasound field effect, solution A is joined in the solution B, stir 5 min, add the 2ml glycinol again, stir and obtain solution C.
(4), the gained solution C is moved in the polytetrafluoroethylene agitated reactor, put into baking oven, at 180 ℃ of reaction 48h down.
(5), gained solution is carried out suction filtration, washing, drying, at last under argon gas atmosphere in 600 ℃ of sintering 6h, obtain the combination product of lithium titanate and Graphene after the cooling.
Embodiment 5
(1), weighing 2,00g hexadecyltrimethylammonium chloride (CTAL), 0.32g urea (CON
2H
4) and 0.96g lithium hydroxide (LiOH.H
2O) be dissolved in the 60ml deionized water, stir 1h, make and contain the stabilizing solution A that lithium concentration is about 0.4mol/L.
(2), under the state of sonicated, in the 23ml deionized water, adding 7ml concentration is the Graphene solution of 0.3g/L, adds the 4.08ml butyl titanate then, ultrasonic 15min stirs 1h, makes to contain the solution B that titanium ion concentration is 0.4mol/L.
(3), under the ultrasound field effect, solution A is joined in the solution B, stir 5 min, add the 2ml glycinol again, obtain solution C.
(4), the gained solution C is moved in the polytetrafluoroethylene agitated reactor, put into baking oven, at 180 ℃ of reaction 48h down.
(5), gained solution is carried out suction filtration, washing, drying, at last under argon gas atmosphere in 600 ℃ of sintering 6h, obtain the combination product of lithium titanate and Graphene after the cooling.
More than through several specific embodiments the present invention has been done detailed explanation, these concrete descriptions can not think that the present invention only is limited to the content of these embodiment.Those skilled in the art conceive according to the present invention, these descriptions and combine any improvement that general knowledge known in this field makes, be equal to replacement scheme, all should be included in the protection range of claim of the present invention.
Claims (9)
1. the preparation method of lithium titanate and graphene combination electrode material is characterized in that may further comprise the steps:
(1), the mol ratio according to surfactant and lithium ion is 0.1 ~ 1:1; The mol ratio of template and lithium ion is 0.05 ~ 0.5:1; The surfactant, template and the lithium compound that take by weighing respective quality are dissolved in the deionized water under stirring condition, make to contain the stabilizing solution A that lithium concentration is 0.1 ~ 5mol/L;
(2), under the ultrasonic wave condition; Mass ratio according to Graphene in the end-product and lithium titanate is the ratio of 1 ~ 30:100, in concentration is the Graphene solution of 0.1 ~ 0.5g/L, adds titanium compound, ultrasonic 15 ~ 30min; Stir 1 ~ 3h, make the solution B that titaniferous concentration is 0.1 ~ 5mol/L;
(3), under the ultrasonic wave effect, solution A is joined in the solution B, stir 5 ~ 60min, adding with product lithium titanate mol ratio is 0.05 ~ 0.5: 1 adhesive again, obtains solution C;
(4), the gained solution C is moved in the polytetrafluoroethylene agitated reactor, put into baking oven, at 140 ~ 200 ℃ of reaction 12 ~ 72h down;
(5), gained solution is carried out suction filtration, washing, drying, at last under argon gas atmosphere in 500 ~ 800 ℃ of sintering 2 ~ 24h, obtain the combination product of lithium titanate and Graphene after the cooling.
2. preparation method as claimed in claim 1 is characterized in that: the mixing time in the said step (1) is 0.5 ~ 5h.
3. preparation method as claimed in claim 2 is characterized in that: described surfactant is selected at least a among softex kw (CTAB), hexadecyltrimethylammonium chloride (CTAL) and the lauryl sodium sulfate three for use.
4. according to claim 1 or claim 2 preparation method, it is characterized in that: described template is selected urea (CON for use
2H
4), at least a among block polymer P123 and the ethylenediamine three.
5. according to claim 1 or claim 2 preparation method is characterized in that: described lithium compound is selected at least a in lithium hydroxide, lithium carbonate, lithia, lithium acetate, lithium oxalate and the lithium chloride for use.
6. according to claim 1 or claim 2 preparation method is characterized in that: described titanium compound is selected at least a in butyl titanate, titanyl sulfate, titanium tetrachloride, Titanium Nitrate, tetraethyl titanate, tetraisopropyl titanate and the metatitanic acid methyl esters for use.
7. according to claim 1 or claim 2 preparation method is characterized in that: described binding agent is selected at least a among hydrazine hydrate, glycinol and the N methyl pyrrolidone three for use.
8. according to claim 1 or claim 2 preparation method, it is characterized in that: the lithium titanate that said step (5) obtains in lithium titanate and the Graphene combination product is the nano-sheet lithium titanate.
9. the lithium titanate and the graphene combination electrode material of each said method preparation of claim 1-8, it is characterized in that: the lithium titanate in this combination electrode material is the nano-sheet lithium titanate, the mass ratio of Graphene and lithium titanate is 1 ~ 30: 100.
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