CN102569769B - 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 47
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 36
- 239000007772 electrode material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 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
- 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
- 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
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 8
- 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
- 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000013066 combination product Substances 0.000 claims description 6
- 229940127555 combination product Drugs 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group 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
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 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
- 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
- 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 17
- 238000002604 ultrasonography Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000007767 bonding agent Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000001035 drying Methods 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
- 239000010936 titanium Substances 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
- 238000005303 weighing Methods 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
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 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
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process 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
- 238000005287 template synthesis Methods 0.000 description 1
Images
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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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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (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, preparation method and the combination electrode material of the compound electrode material of especially a kind of sheet lithium titanate and Graphene.
Background technology
Energy and environment problem is day by day serious, and the development and use of clean energy resource is extremely urgent, and development electric motor car is the inexorable trend of future development.The large-scale application of the green energy resources such as wind energy, solar energy, geothermal energy, has higher requirement to energy storage device, particularly the useful life to energy-storage battery.
Various electronic equipments and electric automobile, hybrid vehicle fast development, proposed harsher requirement to the lithium ion battery that energy is provided for it, particularly its power-performance.Now widely used carbon negative pole material, due to hypopotenia, is easy to electrolyte and reacts, and makes battery system fail safe poor; In addition, carbon negative pole material power-performance is poor, can not solve its fast charging and discharging problem, therefore can not meet 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 electrode material that battery uses.The lithium-ion-power cell of studying is at present conventionally taking LiFePO4, nickel-cobalt-manganese ternary material, LiMn2O4 as positive electrode, material with carbon element is negative material, although the security performance of above-mentioned three kinds of positive electrodes itself is better, but embedding lithium carbon negative pole material in the time that 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.The safety issue of the large-capacity high-power type lithium-ion-power cell that is negative pole with material with carbon element is never effectively solved, seriously restrict its application on electric automobile, having become the fundamental issue of its industrialized development of puzzlement so how to solve the safety issue of lithium-ion-power cell, is also the key issue that hinders electric vehicle industrialization.
The key that solves security of lithium-ion-power cell problem is with safer, less with the electrolyte reactivity alternative carbon negative pole material of negative material.Lithium titanate (Li
4ti
5o
12) there is lot of advantages as a kind of Novel anode material, such as security performance is good, long service life, efficiency for charge-discharge are high, Stability Analysis of Structures etc., potentially be used widely in lithium-ion-power cell field, be considered to most promising lithium ion battery negative material of future generation.And current the faced subject matter of lithium titanate is that intrinsic electronic conductance is low, conductivity is poor, has restricted its application in power-type lithium ion battery as high power negative material.The main path that improves at present the high-rate charge-discharge capability of lithium titanate has three kinds below:
Prepare nanometer particle size Li
4ti
5o
12, mainly prepare by sol-gel process, can obtain nanoscale, the finely dispersed Li of particle
4ti
5o
12particle, complex process, cost is higher, is unfavorable for industrialization;
With the Li of template synthesis porous or hollow structure
4ti
5o
12, can effectively improve electric conductivity and the high-rate charge-discharge capability of material;
By doped with metal elements and the coated Li that improves of carbon
4ti
5o
12the power-performance of electrode material is current the most frequently used method.
Preparation of industrialization Li at present
4ti
5o
12the main method adopting is high temperature solid-state method, and synthetic method is by TiO
2(be mainly Li with lithium source
2cO
3, LiOH and LiNO
3) fully mix, high temperature sintering obtains product.Although solid-phase synthesis technique is simple, cost is low, most products is micron order, and distribution of particles inequality, 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, carbon nano-tube, carbon nanocoils, these methods can improve its high rate performance well, but due to Li wherein
4ti
5o
12be all to exist with three dimensional particles shape, cannot fully contact with a peacekeeping two-dimensional material such as carbon nano-tube, Graphene at compound tense, contact area is limited, has limited the further raising of its performance.
Summary of the invention
The present invention aims to provide synthetic method and the combination electrode material of a kind of lithium titanate and graphene combination electrode material, and Graphene used is the Graphene that this laboratory oneself preparation or market are bought, the Li that this method is synthetic
4ti
5o
12for nano-sheet structure, can contact more fully the feature such as high as power battery cathode material specific capacity, high-rate charge-discharge capability 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 as follows:
(1) be, 0.1 ~ 1:1 according to the mol ratio of surfactant and lithium ion, the mol ratio of template and lithium ion is 0.05 ~ 0.5:1, the surfactant, template and the lithium compound that take respective quality are dissolved in deionized water under the condition stirring, stir 0.5 ~ 5h, the stabilizing solution A that to make containing lithium concentration be 0.1 ~ 5mol/L;
(2), under Ultrasonic Conditions, be 1 ~ 30: 100 ratio according to the mass ratio of Graphene in end-product and lithium titanate, in the graphene solution that is 0.1 ~ 0.5g/L to concentration, add titanium compound, ultrasonic 15 ~ 30min, stir 1 ~ 3h, make the solution B that titaniferous concentration is 0.1 ~ 5mol/L;
(3), under ultrasound field effect, solution A is joined in solution B, stir 5 ~ 60min, then to add with product lithium titanate mol ratio be 0.05 ~ 0.5: 1 adhesive, obtain solution C;
(4), gained solution C is moved in polytetrafluoroethylene reactor, put into baking oven, at 140 ~ 200 DEG C, react 12 ~ 72h;
(5), gained solution is carried out to suction filtration, washing, dry, finally under argon gas atmosphere in 500 ~ 800 DEG C of sintering 2 ~ 24h, obtain end-product after cooling.
Wherein, the preferred softex kw of surfactant (CTAB) using, or hexadecyltrimethylammonium chloride (CTAL), or lauryl sodium sulfate, or two or more combination arbitrarily between them.
Preferred urea (the CON of template using
2h
4), or block polymer P123, or ethylenediamine, or two or more combination arbitrarily between them.
The preferred lithium hydroxide of lithium compound using, or lithium carbonate, or lithia, or lithium acetate, or lithium oxalate, or lithium chloride, or adopt in them the mixture of two or more compositions arbitrarily.
Described titanium compound is selected at least one in butyl titanate, titanyl sulfate, titanium tetrachloride, Titanium Nitrate, tetraethyl titanate, tetraisopropyl titanate and metatitanic acid methyl esters.
Described binding agent is selected at least one in hydrazine hydrate, glycinol and N methyl pyrrolidone three.
The lithium titanate and the graphene combination electrode material that adopt said method to prepare, is characterized in that: the lithium titanate in this combination electrode material is nano-sheet lithium titanate, the mass ratio of Graphene and lithium titanate is 1 ~ 30: 100.
The lithium titanate of preparation method's synthesized of the present invention and graphene combination electrode material make full use of with the compact feature of dimension structural material, utilize prepared nano-sheet lithium titanate, fully mix and contact with the Graphene that is all sheet, have greatly improved Li simultaneously
4ti
5o
12the electronic conductance of material and ionic conductance, 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 preparation process is easily controlled.
Brief description of the drawings
Fig. 1 is the Li making in embodiment 1 and embodiment 2
4ti
5o
12x-ray diffracting spectrum;
Fig. 2 is the Li that embodiment 1 makes
4ti
5o
12shape appearance figure;
Fig. 3 is the shape appearance figure of lithium titanate/Graphene combination product of making of embodiment 2;
Fig. 4 is the Li that embodiment 1 and embodiment 2 make
4ti
5o
12rate charge-discharge performance curve.
Embodiment
embodiment 1
(1), weigh 2.00g softex kw (CTAB), 0.32g urea (CON
2h
4) and 0.96g lithium hydroxide (LiOH.H
2o) be dissolved in 60ml deionized water, stir 1h, make the stabilizing solution A that is about 0.4mol/L containing lithium concentration.
(2), under the state of ultrasonic processing, in 30ml deionized water, add 4.08ml butyl titanate, ultrasonic 15min, stirs 1h, the solution B that to make containing titanium ion concentration be 0.4mol/L.
(3), under ultrasound field effect, solution A is joined in solution B, stir 5 min, then add 5ml hydrazine hydrate, obtain solution C.
(4), gained solution C is moved in polytetrafluoroethylene reactor, put into baking oven, at 180 DEG C, react 48h.
(5), gained solution is carried out to suction filtration, washing, dry, finally under argon gas atmosphere in 600 DEG C of sintering 6h, obtain lithium titanate product after cooling, its shape appearance figure is shown in Fig. 2.
Gained sheet lithium titanate and metal lithium sheet are done to the performance that electrode forms battery test battery.With reference to Fig. 4,10C charging and discharging capacity exceedes 110mAh/g, and 50C charging and discharging capacity reaches 90 mAh/g, and 100C charging and discharging capacity reaches 75mAh/g.
embodiment 2
(1), weighing 2,00g softex kw (CTAB), 0.32g urea (CON
2h
4) and 0.96g lithium hydroxide (LiOH.H
2o) be dissolved in 60ml deionized water, stir 1h, make the stabilizing solution A that is about 0.4mol/L containing lithium concentration.
(2), under the state of ultrasonic processing, be the graphene solution of 0.3g/L to adding 7ml concentration in 23ml deionized water, then add 4.08ml butyl titanate, ultrasonic 15min, stirs 1h, the solution B that to make containing titanium ion concentration be 0.4mol/L.
(3), under ultrasound field effect, solution A is joined in solution B, stir 5 min, then add 5ml hydrazine hydrate, obtain solution C.
(4), gained solution C is moved in polytetrafluoroethylene reactor, put into baking oven, at 180 DEG C, react 48h.
(5), gained solution is carried out to suction filtration, washing, dry, finally under argon gas atmosphere in 600 DEG C of sintering 6h, obtain the combination product of lithium titanate and Graphene after cooling, its shape appearance figure is shown in Fig. 3.
Gained sheet lithium titanate/graphene composite material and metal lithium sheet are done to the performance that electrode forms battery test battery.With reference to Fig. 4, the reversible charging and discharging capacity of 10C exceedes 125mAh/g, and 50C charging and discharging capacity reaches 100 mAh/g, and 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 60ml deionized water, stir 1h, make the stabilizing solution A that is about 0.4mol/L containing lithium concentration.
(2), under the state of ultrasonic processing, be the graphene solution of 0.3g/L to adding 13ml concentration in 17ml deionized water, then add 4.08ml butyl titanate, ultrasonic 15min, stirs 1h, the solution B that to make containing titanium ion concentration be 0.4mol/L.
(3), under ultrasound field effect, solution A is joined in solution B, stir 5 min, then add 5ml hydrazine hydrate, obtain solution C.
(4), gained solution C is moved in polytetrafluoroethylene reactor, put into baking oven, at 180 DEG C, react 48h.
(5), gained solution is carried out to suction filtration, washing, dry, finally under argon gas atmosphere in 600 DEG C of sintering 6h, obtain the combination product of lithium titanate and Graphene after 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 60ml deionized water, stir 1h, make the stabilizing solution A that is about 0.4mol/L containing lithium concentration.
(2), under the state of ultrasonic processing, be the graphene solution of 0.3g/L to adding 4ml concentration in 30ml deionized water, and then add 4.08ml butyl titanate, ultrasonic 15min, stirs 1h, the solution B that to make containing titanium ion concentration be 0.4mol/L.
(3), under ultrasound field effect, solution A is joined in solution B, stir 5 min, then add 2ml glycinol, stir and obtain solution C.
(4), gained solution C is moved in polytetrafluoroethylene reactor, put into baking oven, at 180 DEG C, react 48h.
(5), gained solution is carried out to suction filtration, washing, dry, finally under argon gas atmosphere in 600 DEG C of sintering 6h, obtain the combination product of lithium titanate and Graphene after 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 60ml deionized water, stir 1h, make the stabilizing solution A that is about 0.4mol/L containing lithium concentration.
(2), under the state of ultrasonic processing, be the graphene solution of 0.3g/L to adding 7ml concentration in 23ml deionized water, then add 4.08ml butyl titanate, ultrasonic 15min, stirs 1h, the solution B that to make containing titanium ion concentration be 0.4mol/L.
(3), under ultrasound field effect, solution A is joined in solution B, stir 5 min, then add 2ml glycinol, obtain solution C.
(4), gained solution C is moved in polytetrafluoroethylene reactor, put into baking oven, at 180 DEG C, react 48h.
(5), gained solution is carried out to suction filtration, washing, dry, finally under argon gas atmosphere in 600 DEG C of sintering 6h, obtain the combination product of lithium titanate and Graphene after cooling.
By several specific embodiments, the present invention has been done to detailed explanation above, these concrete descriptions can not think that the present invention only only limits to the content of these embodiment.Those skilled in the art conceive according to the present invention, these descriptions any improvement of making in conjunction with general knowledge known in this field, be equal to replacement scheme, all should be included in the protection range of the claims in the present invention.
Claims (7)
1. a preparation method for lithium titanate and graphene combination electrode material, is characterized in that comprising the following steps:
(1) be, 0.1 ~ 1:1 according to the mol ratio of surfactant and lithium ion, the mol ratio of template and lithium ion is 0.05 ~ 0.5:1, surfactant, template and the lithium compound that takes respective quality is dissolved in deionized water under the condition stirring, the stabilizing solution A that to make containing lithium concentration be 0.1 ~ 5mol/L;
(2), under Ultrasonic Conditions, the ratio that is 1 ~ 30:100 according to the mass ratio of Graphene in end-product and lithium titanate, adds titanium compound in the graphene solution that is 0.1 ~ 0.5g/L to concentration, ultrasonic 15 ~ 30min, stir 1 ~ 3h, make the solution B that titaniferous concentration is 0.1 ~ 5mol/L;
(3), under ul-trasonic irradiation, solution A is joined in solution B, stir 5 ~ 60min, then to add with product lithium titanate mol ratio be 0.05 ~ 0.5: 1 adhesive, obtain solution C;
(4), gained solution C is moved in polytetrafluoroethylene reactor, put into baking oven, at 140 ~ 200 DEG C, react 12 ~ 72h; (5), gained solution is carried out to suction filtration, washing, dry, finally under argon gas atmosphere in 500 ~ 800 DEG C of sintering 2 ~ 24h, obtain the combination product of nano-sheet lithium titanate and Graphene after cooling;
Described in step (1), template is urea or ethylenediamine;
Described in step (3), adhesive is hydrazine hydrate or glycinol.
2. preparation method as claimed in claim 1, is characterized in that: the mixing time in described step (1) is 0.5 ~ 5h.
3. preparation method as claimed in claim 2, is characterized in that: described surfactant is selected at least one in softex kw (CTAB), hexadecyltrimethylammonium chloride (CTAL) and lauryl sodium sulfate three.
4. preparation method as claimed in claim 1 or 2, is characterized in that: described template substitutes with block polymer P123.
5. preparation method as claimed in claim 1 or 2, is characterized in that: described lithium compound is selected at least one in lithium hydroxide, lithium carbonate, lithia, lithium acetate, lithium oxalate and lithium chloride.
6. preparation method as claimed in claim 1 or 2, is characterized in that: described titanium compound is selected at least one in butyl titanate, titanyl sulfate, titanium tetrachloride, Titanium Nitrate, tetraethyl titanate, tetraisopropyl titanate and metatitanic acid methyl esters.
7. described in claim 1-6 any one prepared by method lithium titanate and graphene combination electrode material, is characterized in that: the lithium titanate in this combination electrode material is nano-sheet lithium titanate, and the mass ratio of Graphene and lithium titanate is 1 ~ 30: 100.
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