CN103151505A - Lithium-titanate composite negative pole material and preparation method thereof - Google Patents
Lithium-titanate composite negative pole material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a lithium-titanate composite negative pole material and a preparation method thereof. The lithium-titanate composite negative pole material provided by the invention comprises lithium titanate, doping elements and a graphene/carbon nanotube composite material. The preparation method comprises the following steps: preparing a titanium source, a lithium source, soluble compounds of doping elements and the graphene/carbon nanotube composite material into a precursor by sol-gel in-situ synthesis, and calcining the precursor at 400-1100 DEG C to obtain the lithium-titanate composite negative pole material. The graphene/carbon nanotube composite material is utilized to effectively improve the electronic conductivity and rate capability of the lithium-titanate negative pole material; and the doping elements are introduced to effectively enhance the electrochemical properties and loop stability of the lithium-titanate negative pole material. The lithium-titanate negative pole material provided by the invention has wide application prospects in the field of lithium ion batteries.
Description
Technical field
The present invention relates to lithium ion battery and ultracapacitor technical field, particularly, the present invention relates to a kind of lithium titanate is composite negative pole material and preparation method thereof.
Background technology
Negative material is one of critical material of lithium ion battery, at present, lithium ion battery negative material used mostly is greatly the lithium intercalated graphite material with carbon element, but there are some problems in actual applications in this class material, as, first charge-discharge efficiency is lower, the charge and discharge process volume changes, and easily forms Li dendrite and causes short circuit, makes electrolyte decomposition have potential safety hazard etc.By contrast, lithium titanate with spinel structure, its theoretical capacity is 175mAh/g, lithium ion inserts and takes off embedding to almost not impact of material structure in charge and discharge process, is called " zero strain " material, and the good and platform capacity of charge and discharge platform can reach more than 90% of discharge capacity, good cycle, with the electrolyte reaction, the preparation method is not simple, and cost is lower.Therefore, spinel type lithium titanate has become the extremely wide lithium ion battery negative material of commercial applications prospect with its excellent security feature and long circulation life at present.
Although lithium titanate has many outstanding advantages as lithium ion battery negative material, and the chemical diffusion coefficient of lithium ion is 2 * 10 at normal temperatures
-8cm
2/ s, than order of magnitude of carbon negative maximum, still, its intrinsic conductivity is lower, is only 10
-9S/cm belongs to typical insulator, poorly conductive, thereby when causing high power charging-discharging poor-performing and special capacity fade very fast, heavy-current discharge performance is undesirable.Can improve the electric conductivity of material by doping, to obtain fast charging and discharging performance and cycle performance preferably.Chinese invention patent " a kind of lithium titanate anode material of yttrium modification is the preparation method extremely " (CN102780005A), this patent adopts solid phase method to prepare a kind of lithium titanate anode material of yttrium modification, has good chemical property and higher coulombic efficiency.Chinese invention patent " a kind of lithium titanate anode material of the lanthanum that adulterates is the preparation method extremely " (CN102637864A), this patent adopts solid phase method to prepare the lithium titanate anode material of lanthanum doping, by doping Trace La refinement crystal grain, improved the chemical property of lithium titanate.The mode of above-mentioned two kinds of single metal ions of doping has all obtained useful effect, thereby but easily producing raw material when adopting solid phase method to prepare mixes the inhomogeneous problem that affects chemical property.Chinese invention patent " a kind of three-dimensional porous Graphene doping and the preparation method who coats the lithium titanate composite negative pole material " (CN102646810A), disclose a kind of three-dimensional porous Graphene doping and the preparation method who coats lithium titanate composite material, effectively improved the high magnification chemical property of lithium titanate anode material by the doping carbon material.But the three-dimensional porous grapheme material described in this patent is processed by hydro thermal method, still can not effectively suppress the stacking and agglomeration in sintering process perhaps of the lamella of Graphene, and this has limited the performance of its performance to a certain extent.
Therefore, develop a kind of preparation method simple, excellent electric conductivity, under high magnification, chemical property is good, and the lithium titanate with good electrochemistry cyclical stability is that negative material is an affiliated art difficult problem.
Summary of the invention
For the deficiencies in the prior art, it is composite negative pole material that one of purpose of the present invention is to provide a kind of lithium titanate, and it has good electronics and lithium ion conductive, and under high magnification, chemical property is good, has good electrochemistry cyclical stability.
Described lithium titanate is that composite negative pole material comprises: lithium titanate, doped chemical and graphene/carbon nanometer tube composite materials.
In the present invention, if no special instructions, "/" refer to " with ", for example described " graphene/carbon nanometer tube composite materials " refers to the composite material that Graphene and carbon nano-tube form.
The preparation method of described graphene/carbon nanometer tube composite materials can be any prior art, for example simply mixes, and also can adopt other method preparation, and one of ordinary skill in the art can select as required.
Preferably, described lithium titanate is that composite negative pole material is comprised of lithium titanate, doped chemical and graphene/carbon nanometer tube composite materials.
Preferably, described lithium titanate is that described lithium titanate is 80.0 ~ 99.8% of composite negative pole material quality, such as: 80.1%, 80.2%, 81.0%, 84.0%, 86.0%, 87.0%, 89.0%, 95.0%, 98.1%, 99.0%, 99.5%, 99.6% or 99.7% etc., more preferably 85.0 ~ 99.8%, be particularly preferably 88.0 ~ 99.8%.
Preferably, described doped chemical is that described lithium titanate is 0.01 ~ 5.0% of composite negative pole material quality, such as: 0.02%, 0.03%, 0.05%, 0.1%, 0.2%, 0.5%, 1.0%, 1.5%, 1.9%, 2.1%, 2.5%, 2.9%, 3.1%, 3.5%, 4.0%, 4.5%, 4.8% or 4.9% etc., more preferably 0.01 ~ 3.0%, be particularly preferably 0.01 ~ 2.0%.
Preferably, described graphene/carbon nanometer tube composite materials is that described lithium titanate is 0.01 ~ 16.0% of composite negative pole material quality, such as: 0.02%, 0.03%, 0.05%, 0.1%, 0.2%, 0.5%, 1.0%, 3.0%, 5.0%, 7.0%, 9.0%, 11.0%, 11.9%, 12.1%, 13.0%, 14.0%, 15.0%, 15.5%, 15.8% or 15.9% etc., more preferably 0.01 ~ 12.0%, be particularly preferably 0.01 ~ 10.0%.
In one embodiment, described lithium titanate is that composite negative pole material comprises: lithium titanate, doped chemical and graphene/carbon nanometer tube composite materials, wherein, described lithium titanate is that described lithium titanate is 80.0 ~ 99.8% of composite negative pole material quality, described doped chemical is that described lithium titanate is 0.01 ~ 5.0% of composite negative pole material quality, and described graphene/carbon nanometer tube composite materials is that described lithium titanate is 0.01 ~ 16.0% of composite negative pole material quality.
In another embodiment, described lithium titanate is that composite negative pole material is comprised of lithium titanate, doped chemical and graphene/carbon nanometer tube composite materials, wherein, described lithium titanate is that described lithium titanate is 80.0 ~ 99.8% of composite negative pole material quality, described doped chemical is that described lithium titanate is 0.01 ~ 5.0% of composite negative pole material quality, and described graphene/carbon nanometer tube composite materials is that described lithium titanate is 0.01 ~ 16.0% of composite negative pole material quality.
Preferably, described doped chemical is a kind or the combination of at least 2 kinds in Ru, Co, La, Mg, Zr, Ni, Mn, Y, Ag, Ca, Nb, Sr, V, Zn, Ta, Sn, Cr, Al, Ga or Cu, the typical but non-limiting example of described combination comprises: the combination of Ru and Co, the combination of Zr and Ni, the combination of La, Mg and Zr, the combination of Co, Ag and Ca, the combination of Ru, Co, La and Mg, the combination of Ni, Mn, Y and Ag, the combination of Ca, Nb, Sr, V and Zn, the combination of Ta, Sn, Cr, Al, Ga and Cu etc.
Preferably, described Graphene accounts for 0.01 ~ 70.0% of graphene/carbon nanometer tube composite materials gross mass, such as 0.02%, 0.03%, 0.05%, 0.1%, 0.2%, 1.0%, 2.0%, 5.0%, 10.0%, 20.0%, 40.0%, 45.0%, 49.0%, 51.0%, 55.0%, 59.0%, 61.0%, 65.0%, 68.0% or 69.0% etc., more preferably 0.01 ~ 60.0%, be particularly preferably 0.01 ~ 50.0%.
It is the preparation method of composite negative pole material that one of purpose of the present invention also is to provide a kind of described lithium titanate, and described method is the in-situ doped method of sol-gel.
Described lithium titanate is that the preparation method of composite negative pole material comprises the following steps:
(1) lithium source, titanium source, chelating agent and doped chemical source are dispersed in medium, obtain mixed dispersion liquid;
(2) mixed dispersion liquid that step (1) is obtained is mixed with graphene/carbon nanometer tube composite materials dispersion liquid, obtains Gel Precursor;
(3) Gel Precursor that step (2) is obtained is dry, and then 400 ~ 1100 ℃ of calcinings, obtaining lithium titanate is composite negative pole material.
Preferably, described step (1) comprising: lithium source, titanium source and chelating agent are dispersed in obtain dispersion liquid A in solvent, dispersion liquid A is mixed with doped chemical source dispersion liquid, obtain mixed dispersion liquid; Preferably, described dispersion is under agitation carried out; Preferably, described being mixed into dropwise is added to dispersion liquid A in the dispersion liquid of doped chemical source, and stirs at least 0.2 hour, and more preferably 0.3 ~ 1 hour, particularly preferably 0.5 hour; Preferably, the concentration of lithium in dispersion liquid A is 0.01 ~ 3.0mol/L, and more preferably 0.05 ~ 2.0mol/L, be particularly preferably 0.1 ~ 1.0mol/L; Preferably, described doped chemical source dispersion liquid is the aqueous solution in doped chemical source; Preferably, in the dispersion liquid of described doped chemical source, the concentration in doped chemical source is 0.01～1mol/L, such as 0.02mol/L, 0.03mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.6mol/L, 0.65mol/L, 0.69mol/L, 0.71mol/L, 0.75mol/L, 0.8mol/L, 0.9mol/L, 0.95mol/L, 0.98mol/L or 0.99mol/L etc., more preferably 0.01～0.7mol/L, be particularly preferably 0.01～0.5mol/L; Preferably, described solvent is water and/or organic solvent, more preferably water, ethanol, ethylene glycol, normal propyl alcohol, isopropyl alcohol, glycerol, acetone, methylethylketone, CCl
4Or a kind or the combination of at least 2 kinds in toluene, the typical but non-limiting example of described combination comprises: the combination of water and ethanol, the combination of ethylene glycol and normal propyl alcohol, the combination of isopropyl alcohol, glycerol and acetone, the combination of ethanol, ethylene glycol, acetone and toluene, isopropyl alcohol, glycerol, acetone, CCl
4With combination of toluene etc., be particularly preferably a kind or the combination of at least 2 kinds in deionized water, acetone, ethanol or isopropyl alcohol.
Preferably, step (2) comprising: add graphene/carbon nanometer tube composite materials dispersion liquid in the mixed dispersion liquid that step (1) obtains, and first the stirring, ultrasonic processing is afterwards stirred again, obtains Gel Precursor; Preferably, described first mixing time is at least 0.5 hour, more preferably 0.8 ~ 5 hour, is particularly preferably 1 hour; Preferably, the described ultrasonic processing time is at least 0.2 hour, more preferably 0.3 ~ 5 hour, is particularly preferably 0.5 ~ 1 hour; Preferably, described again being stirred under 50 ~ 140 ℃ carried out, and more preferably 60 ~ 130 ℃, is particularly preferably 80 ~ 120 ℃.
Preferably, the mol ratio of the described lithium of step (1) and titanium is 3:5 ~ 10:5, and more preferably 4:5 ~ 6:5, be particularly preferably 4:5.
Preferably, the mol ratio of the described titanium of step (1) and chelating agent is 1:0.05 ~ 1:1, and more preferably 1:0.08 ~ 1:0.7, be particularly preferably 1:0.1 ~ 1:0.5.
Preferably, described dispersion is dissolving independently.
preferably, described titanium source is butyl titanate, isopropyl titanate, titanium tetrachloride, titanyl sulfate, 1 kind or the combination of at least 2 kinds in metatitanic acid methyl esters or iso-butyl titanate, the typical but non-limiting example of described combination has: the combination of butyl titanate and isopropyl titanate, the combination of titanyl sulfate and metatitanic acid methyl esters, isopropyl titanate, the combination of titanium tetrachloride and titanyl sulfate, titanium tetrachloride, titanyl sulfate, the combination of metatitanic acid methyl esters and iso-butyl titanate, butyl titanate, isopropyl titanate, titanium tetrachloride, the combination of titanyl sulfate and metatitanic acid methyl esters, butyl titanate, isopropyl titanate, titanium tetrachloride, titanyl sulfate, the combination of metatitanic acid methyl esters and iso-butyl titanate etc.
preferably, described lithium source is lithium dihydrogen phosphate, lithium carbonate, lithium acetate, lithium formate, lithium citrate, lithium chloride, lithium nitrate, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium oxalate, 1 kind or the combination of at least 2 kinds in lithium sulfate, the typical but non-limiting example of described combination has: the combination of lithium dihydrogen phosphate and lithium carbonate, the combination of lithium carbonate and lithium acetate, the combination of lithium chloride and lithium nitrate, lithium acetate, the combination of lithium formate and lithium citrate, lithium hydroxide, the combination of tert-butyl alcohol lithium and lithium oxalate, lithium nitrate, lithium bromide, the combination of lithium hydroxide and tert-butyl alcohol lithium, lithium hydroxide, tert-butyl alcohol lithium, the combination of lithium benzoate and phosphoric acid hydrogen two lithiums, lithium phosphate, phosphoric acid hydrogen two lithiums, the combination of lithium oxalate and lithium sulfate, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, the combination of lithium phosphate and phosphoric acid hydrogen two lithiums, lithium chloride, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, the combinations of lithium phosphate and phosphoric acid hydrogen two lithiums etc. are particularly preferably lithium acetate, lithium hydroxide, lithium nitrate, 1 kind or the combination of at least 2 kinds in lithium chloride or lithium sulfate.
Preferably, described doped chemical source is the soluble-salt of doped chemical, is particularly preferably doped chemical nitrate and/or doped chemical acetate.
Preferably, described chelating agent is a kind or the combination of at least 2 kinds in glacial acetic acid, tartaric acid, oxalic acid, citric acid or acrylic acid, the typical but non-limiting example of described combination has: glacial acetic acid and tartaric combination, the combination of oxalic acid and citric acid, glacial acetic acid, oxalic acid and acrylic acid combination, tartaric acid, oxalic acid, citric acid and acrylic acid combination, glacial acetic acid, tartaric acid, oxalic acid, citric acid and acrylic acid combination etc. are particularly preferably citric acid.
Preferably, the described graphene/carbon nanometer tube composite materials of step (2) dispersion liquid is the ethanolic solution of graphene/carbon nanometer tube composite materials.
Preferably, in the described graphene/carbon nanometer tube composite materials of step (2) dispersion liquid, the concentration of graphene/carbon nanometer tube composite materials is 0.01～12g/L, and more preferably 0.05～10g/L, be particularly preferably 0.1～6g/L.
Preferably, carry out refinement before the described calcining of step (3).
Preferably, carry out refinement after the described calcining of step (3).
Preferably, the described calcining of step (3) is carried out under inert atmosphere; Described inert atmosphere is a kind or the combination of at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton or xenon for example, the mixed atmosphere of helium and nitrogen for example, the mixed atmosphere of helium and neon, the mixed atmosphere of nitrogen, argon gas and Krypton, the mixed atmosphere of argon gas, Krypton and xenon, the mixed atmosphere of xenon, nitrogen, helium and neon, the mixed atmosphere of nitrogen, helium, neon and argon gas, the mixed atmospheres of nitrogen, helium, neon, argon gas and Krypton etc. are particularly preferably nitrogen and/or argon gas.
Preferably, the described calcining heat of step (3) is 450 ~ 1000 ℃, is particularly preferably 500 ~ 950 ℃.
Preferably, the described calcination time of step (3) is at least 1 hour, more preferably 2 ~ 48 hours, is particularly preferably 3 ~ 24 hours.
Preferably, the preparation method of described graphene/carbon nanometer tube composite materials comprises the following steps:
A) carbon nano-tube acidifying;
B) with the carbon nano-tube after graphene oxide, acidifying and solvent, then with the reducing agent reaction, removal of impurities obtains the graphene/carbon nanometer tube composite materials.
Described cabonic acid turns to prior art, and one of ordinary skill in the art can select as required.
Preferably, described step a) comprises: the mixed acid that carbon nano-tube is placed in the concentrated sulfuric acid and red fuming nitric acid (RFNA), wherein, the mass ratio of mixed acid and carbon nano-tube is more than 20:1, the mass ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 2:1 ~ 4:1, then disperses, 90 ~ 150 ℃ of reactions, last removal of impurities obtains the carbon nano-tube after acidifying; Preferably, the mass ratio of described mixed acid and carbon nano-tube is 30:1 ~ 60:1, is particularly preferably 40:1; Preferably, the mass ratio of the described concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3:1; Preferably, describedly be separated into ultrasonic dispersion; Preferably, described jitter time is 0.2 ~ 3 hour, more preferably 0.3 ~ 2 hour, is particularly preferably 0.5 ~ 1 hour; Preferably, described reaction temperature is 95 ~ 140 ℃, is particularly preferably 100 ~ 130 ℃; Preferably, the described reaction time is at least 0.5 hour, more preferably 0.8 ~ 5 hour, is particularly preferably 1 ~ 2 hour; Preferably, described removal of impurities comprises: solution distilled water diluting after reacting, remove the upper strata stillness of night, and repeatedly rinse for several times, be the polyethylene microporous membrane suction filtration of 0.2 μ m with the aperture, be washed to neutrality, last vacuumize.
In the present invention, the described concentrated sulfuric acid refers to that mass fraction is more than or equal to 70% sulfuric acid solution; Described red fuming nitric acid (RFNA) refers to that mass fraction is more than or equal to 60% salpeter solution.
Preferably, the described solvent of step b) is water and/or organic solvent, is particularly preferably deionized water.
Preferably, the gross mass of the carbon nano-tube after step b) graphene oxide and acidifying and the mass ratio of described solvent are below 1:100, and more preferably 1:300 ~ 1:100, be particularly preferably 1:200.
Preferably, the described mixing of step b) comprises ultrasonic and stirring successively; Preferably, described ultrasonic time is at least 0.2 hour, more preferably 0.3 ~ 1 hour, is particularly preferably 0.5 hour; Preferably, described mixing time is at least 0.2 hour, more preferably 0.3 ~ 1 hour, is particularly preferably 0.5 hour.
Preferably, the described reducing agent of step b) is a kind or the combination of at least 2 kinds in hydrazine, phenylhydrazine, ascorbic acid, sodium borohydride, p-phenylenediamine (PPD), ammoniacal liquor, Cys, glutathione or vitamin C, more preferably a kind in hydrazine, phenylhydrazine, sodium borohydride or p-phenylenediamine (PPD) or the combination of at least 2 kinds, be particularly preferably hydrazine.
Preferably, the gross mass of the carbon nano-tube after step b) graphene oxide and acidifying and the mass ratio of described reducing agent are below 1:5, and more preferably 1:8 ~ 1:20, be particularly preferably 1:10.
Preferably, the described reaction of step b) is under agitation carried out.
Preferably, the described reaction time of step b) is at least 10 hours, more preferably 12 ~ 48 hours, is particularly preferably 15 ~ 30 hours.
Preferably, the described removal of impurities of step b) comprises: be the polyethylene microporous membrane suction filtration of 0.2 μ m with the aperture, and washing, final drying.
Preferably, described lithium titanate is that the preparation method of composite negative pole material comprises the following steps:
(1) lithium source, titanium source and chelating agent are dispersed in obtain dispersion liquid A in solvent, wherein, the concentration of lithium is 0.01 ~ 3.0mol/L, and the mol ratio of lithium and titanium is 3:5 ~ 10:5, and the mol ratio of titanium and chelating agent is 1:0.05 ~ 1:1; Dispersion liquid A dropwise is added in the doped chemical source dispersion liquid of 0.01～1mol/L, mixes, obtain mixed dispersion liquid;
(2) mixed dispersion liquid that step (1) is obtained is mixed with the ethanolic solution of the graphene/carbon nanometer tube composite materials of 0.01～12g/L, stirs successively and ultrasonic processing, then continues to stir until obtain Gel Precursor at 50 ~ 140 ℃;
(3) after the Gel Precursor drying that step (2) is obtained, refinement obtains precursor powder, then in inert gas through 400 ~ 1100 ℃ of calcinings at least 1 hour, obtaining lithium titanate after refinement is composite negative pole material.
Adopting the lithium titanate of the method for the invention preparation is composite negative pole material, and doped chemical, lithium, titanium and graphene/carbon nanotube complex carbon material mix, and making lithium titanate is that composite negative pole material has excellent chemical property.
Outstanding advantages of the present invention and good effect are as follows:
(1) to adopt the lithium titanate of the standby metallic element of the in-situ doped legal system of sol-gel and the modification of graphene/carbon nanotube complex carbon material co-doped be composite negative pole material in the present invention, compare with the solid phase method doping, the soluble compound of metallic element, lithium source and titanium source can reach the even mixing of molecular level in preparation process, can effectively improve the chemical property (its first discharge specific capacity is greater than 158mAh/g under the multiplying power of 1C) of composite negative pole material.
(2) the present invention is the graphene/carbon nanotube complex carbon material that adulterated in the process of composite negative pole material at the preparation lithium titanate, this complex carbon material has played the effect of electric transmission resilient coating in negative material, can increase the lithium ion diffusion coefficient of lithium titanate composite negative pole material, effectively improve its cycle performance, with this negative material make electrode diaphragm and and metal lithium sheet be assembled into battery, find afterwards after tested, the capability retention after circulation under the 0.5C multiplying power 50 times is greater than 98%.
(3) in the graphene/carbon nanotube complex carbon material that provides in the present invention, Graphene is kept apart by carbon nano-tube is well-proportioned, effectively avoided Graphene after drying and with the lithium titanate recombination process in lamination and agglomeration, to have increased substantially lithium titanate be the chemical property of composite negative pole material.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
The lithium titanate of following examples preparation is that the method for testing of composite negative pole material is as follows:
With the lithium titanate of preparation be composite negative pole material, acetylene black and Kynoar according to the quality of 95:5:5 than weighing after, mode and 1-METHYLPYRROLIDONE by ultrasonic dispersion and rapid stirring are mixed with uniform sizing material, through being coated in after froth in vacuum on the collector aluminium foil, flatten on roll squeezer after 80 ℃ of dryings and make electrode diaphragm, this diaphragm is washed into the disk that diameter is 9mm, it is assembled into button cell with the lithium sheet after 120 ℃ of vacuumize 12h, electrolyte adopts the LiPF that contains 1mol/L
6Ethyl carbonate and the mixed liquor of dimethyl carbonate (volume ratio 1:1).Carry out charge-discharge test after this button cell is placed 24h in the voltage range of 1～2.5V, its first discharge specific capacity is greater than 158mAh/g under the multiplying power of 1C.
Embodiment 1
The carbon nano-tube acidifying: the appropriate carbon nano-tube of weighing is placed in there-necked flask, add a certain amount of concentrated sulfuric acid and red fuming nitric acid (RFNA), the mass ratio that makes both is 3:1, and the gross mass of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 40 times of carbon nano-tube, ultrasonic dispersion 0.5h, the 2h that refluxes in the oil bath of 100 ℃ with the solution distilled water diluting, removes the upper strata stillness of night, repeatedly rinse for several times, be the polyethylene microporous membrane suction filtration of 0.2 μ m with the aperture, be washed to neutrality, obtain the carbon nano-tube of acidifying after vacuumize.
the preparation of graphene/carbon nanometer tube composite materials: take appropriate graphene oxide and the carbon nano-tube after acidification, the quality percentage composition that makes Graphene in the graphene/carbon nanometer tube composite materials is 0.01%, adding mass content is the deionized water of 200 times of carbon nano-tube gross masses after graphene oxide and acidifying, ultrasonic 0.5h, rapid stirring 0.5h, adding mass content is the hydrazine of 10 times of carbon nano-tube gross masses after graphene oxide and acidifying, continue to stir and make it to react 30h, it is the polyethylene microporous membrane suction filtration of 0.2 μ m with the aperture, washing, obtain the graphene/carbon nanometer tube composite materials after dry.
Lithium titanate is the preparation of composite negative pole material: lithium acetate, butyl titanate and citric acid are dissolved in rapid stirring in appropriate solvent until form homogeneous solution A, wherein, the molar concentration of lithium ion is 0.1mol/L, and the mol ratio of lithium and titanium is 4:5, and the mol ratio of titanium and citric acid is 1:0.1.Dropwise adding total concentration in the solution A is the lanthanum nitrate of 0.5mol/L and the aqueous solution of strontium nitrate, and the gross mass that makes lanthanum and strontium element is that lithium titanate is 2.0% of composite negative pole material gross mass, and rapid stirring 0.5h gets solution B.The ethanolic solution that adds the graphene/carbon nanometer tube composite materials of 6g/L in the solution B, the gross mass that makes the graphene/carbon nanometer tube composite materials is that lithium titanate is 10.0% of composite negative pole material gross mass, continue to stir 1h and ultrasonic processing 0.5h, then continue rapid stirring until obtain Gel Precursor at 120 ℃, refinement after this Gel Precursor drying is obtained precursor powder, then with this powder in the mist of nitrogen and argon gas through 950 ℃ of calcining 3h, obtaining lithium titanate after refinement is composite negative pole material.
With above-mentioned lithium titanate be composite negative pole material, acetylene black and Kynoar according to the quality of 95:5:5 than weighing after mode and 1-METHYLPYRROLIDONE by ultrasonic dispersion and rapid stirring be mixed with uniform sizing material, through being coated in after froth in vacuum on the collector aluminium foil, flatten on roll squeezer after 80 ℃ of dryings and make electrode diaphragm, this diaphragm is washed into the disk that diameter is 9mm, it is assembled into button cell with the lithium sheet after 120 ℃ of vacuumize 12h, electrolyte adopts the LiPF that contains 1mol/L
6Ethyl carbonate and the mixed liquor of dimethyl carbonate (volume ratio 1:1).Carry out charge-discharge test after this button cell is placed 24h in the voltage range of 1～2.5V, its first discharge specific capacity is 171.5mAh/g under the multiplying power of 1C.
Embodiment 2
First with the carbon nano-tube acidifying, method is with embodiment 1, that different is ultrasonic 1h in acidization, 1h refluxes in the oil bath of 130 ℃, then prepare the graphene/carbon nanometer tube composite materials, method is with embodiment 1, and the quality percentage composition of different is Graphene in the graphene/carbon nanometer tube composite materials is 50%, adds hydrazine afterreaction 26h.
Lithium titanate is the preparation of composite negative pole material: lithium hydroxide, titanium tetrachloride and citric acid are dissolved in rapid stirring in appropriate solvent until form homogeneous solution A, wherein, the molar concentration of lithium ion is 0.5mol/L, and the mol ratio of lithium and titanium is 4:5, and the mol ratio of titanium and citric acid is 1:0.5.Dropwise adding total concentration in the solution A is the calcium nitrate of 0.01mol/L and the aqueous solution of nickel nitrate, and the gross mass that makes calcium and nickel element is that lithium titanate is 1.0% of composite negative pole material gross mass, and rapid stirring 0.5h gets solution B.The ethanolic solution that adds the graphene/carbon nanometer tube composite materials of 0.1g/L in the solution B, the gross mass that makes the graphene/carbon nanometer tube composite materials is that lithium titanate is 0.01% of composite negative pole material gross mass, continue to stir 1h and ultrasonic processing 1h, then continue rapid stirring until obtain Gel Precursor at 80 ℃, refinement after this Gel Precursor drying is obtained precursor powder, then with this powder in nitrogen through 500 ℃ of calcining 24h, obtaining lithium titanate after refinement is composite negative pole material.
Being composite negative pole material with above-mentioned lithium titanate prepares button cell according to the method for embodiment 1, carries out charge-discharge test after will this button cell placing 24h in the voltage range of 1～2.5V, and its first discharge specific capacity is 171.5mAh/g under the multiplying power of 1C.
Embodiment 3
First with the carbon nano-tube acidifying, method is with embodiment 1, that different is ultrasonic 0.6h in acidization, 1.5h refluxes in the oil bath of 120 ℃, then prepare the graphene/carbon nanometer tube composite materials, method is with embodiment 1, and the quality percentage composition of different is Graphene in the graphene/carbon nanometer tube composite materials is 20%, adds hydrazine afterreaction 20h.
Lithium titanate is the preparation of composite negative pole material: lithium nitrate, isopropyl titanate and citric acid are dissolved in rapid stirring in appropriate solvent until form homogeneous solution A, wherein, the molar concentration of lithium ion is 0.8mol/L, and the mol ratio of lithium and titanium is 4:5, and the mol ratio of titanium and citric acid is 1:0.3.Dropwise add the aqueous solution of 0.1mol/L ruthenic chloride in the solution A, the quality that makes ruthenium element is that lithium titanate is 0.5% of composite negative pole material gross mass, and rapid stirring 0.5h gets solution B.The ethanolic solution that adds the graphene/carbon nanometer tube composite materials of 1.0g/L in the solution B, the gross mass that makes the graphene/carbon nanometer tube composite materials is that lithium titanate is 3.0% of composite negative pole material gross mass, continue to stir 1h and ultrasonic processing 1h, then continue rapid stirring until obtain Gel Precursor at 100 ℃, refinement after this Gel Precursor drying is obtained precursor powder, then with this powder in argon gas through 650 ℃ of calcining 20h, obtaining lithium titanate after refinement is composite negative pole material.
Being composite negative pole material with above-mentioned lithium titanate prepares button cell according to the method for embodiment 1, carries out charge-discharge test after will this button cell placing 24h in the voltage range of 1～2.5V, and its first discharge specific capacity is 163.2mAh/g under the multiplying power of 1C.
Embodiment 4
First with the carbon nano-tube acidifying, then method prepares the graphene/carbon nanometer tube composite materials with embodiment 1, and method is with embodiment 1, and the quality percentage composition of different is Graphene in the graphene/carbon nanometer tube composite materials is 35%, adds hydrazine afterreaction 24h.
Lithium titanate is the preparation of composite negative pole material: lithium chloride, iso-butyl titanate and citric acid are dissolved in rapid stirring in appropriate solvent until form homogeneous solution A, wherein, the molar concentration of lithium ion is 1.0mol/L, and the mol ratio of lithium and titanium is 4:5, and the mol ratio of titanium and citric acid is 1:0.4.Dropwise adding total concentration in the solution A is the cobalt acetate of 0.3mol/L and the aqueous solution of magnesium acetate, and the gross mass that makes cobalt and magnesium elements is that lithium titanate is 1.5% of composite negative pole material gross mass, and rapid stirring 0.5h gets solution B.The ethanolic solution that adds the graphene/carbon nanometer tube composite materials of 3.0g/L in the solution B, the gross mass that makes the graphene/carbon nanometer tube composite materials is that lithium titanate is 7.0% of composite negative pole material gross mass, continue to stir 1h and ultrasonic processing 1h, then continue rapid stirring until obtain Gel Precursor at 110 ℃, refinement after this Gel Precursor drying is obtained precursor powder, then with this powder in argon gas through 800 ℃ of calcining 15h, obtaining lithium titanate after refinement is composite negative pole material.
Being composite negative pole material with above-mentioned lithium titanate prepares button cell according to the method for embodiment 1, carries out charge-discharge test after will this button cell placing 24h in the voltage range of 1～2.5V, and its first discharge specific capacity is 168.6mAh/g under the multiplying power of 1C.
Embodiment 5
The carbon nano-tube acidifying: the appropriate carbon nano-tube of weighing is placed in there-necked flask, add a certain amount of concentrated sulfuric acid and red fuming nitric acid (RFNA), the mass ratio that makes both is 2:1, and the gross mass of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 20 times of carbon nano-tube, ultrasonic dispersion 3h, the 6h that refluxes in the oil bath of 90 ℃ with the solution distilled water diluting, removes the upper strata stillness of night, repeatedly rinse for several times, be the polyethylene microporous membrane suction filtration of 0.2 μ m with the aperture, be washed to neutrality, obtain the carbon nano-tube of acidifying after vacuumize.
the preparation of graphene/carbon nanometer tube composite materials: take appropriate graphene oxide and the carbon nano-tube after acidification, the quality percentage composition that makes Graphene in the graphene/carbon nanometer tube composite materials is 70.0%, adding mass content is the deionized water of 100 times of carbon nano-tube gross masses after graphene oxide and acidifying, ultrasonic 0.2h, rapid stirring 1h, adding mass content is the p-phenylenediamine (PPD) of 5 times of carbon nano-tube gross masses after graphene oxide and acidifying, continue to stir and make it to react 10h, it is the polyethylene microporous membrane suction filtration of 0.2 μ m with the aperture, washing, obtain the graphene/carbon nanometer tube composite materials after dry.
Lithium titanate is the preparation of composite negative pole material: tert-butyl alcohol lithium, lithium acetate, titanyl sulfate, citric acid and oxalic acid are dissolved in rapid stirring in appropriate solvent until form homogeneous solution A, wherein, the molar concentration of lithium ion is 3.0mol/L, the mol ratio of lithium and titanium is 10:5, and the mol ratio of titanium and oxalic acid is 1:1.Dropwise adding total concentration in the solution A is the zinc chloride of 1mol/L and the aqueous solution of manganese chloride, and the gross mass that makes zinc and manganese element is that lithium titanate is 5.0% of composite negative pole material gross mass, and rapid stirring 1h gets solution B.The ethanolic solution that adds the graphene/carbon nanometer tube composite materials of 0.01g/L in the solution B, the gross mass that makes the graphene/carbon nanometer tube composite materials is that lithium titanate is 0.01% of composite negative pole material gross mass, continue to stir 0.5h and ultrasonic processing 5h, then continue rapid stirring until obtain Gel Precursor at 50 ℃, refinement after this Gel Precursor drying is obtained precursor powder, then with this powder in helium through 1100 ℃ of calcining 1h, obtaining lithium titanate after refinement is composite negative pole material.
Being composite negative pole material with above-mentioned lithium titanate prepares button cell according to the method for embodiment 1, carries out charge-discharge test after will this button cell placing 24h in the voltage range of 1～2.5V, and its first discharge specific capacity is 166.4mAh/g under the multiplying power of 1C.
Embodiment 6
The carbon nano-tube acidifying: the appropriate carbon nano-tube of weighing is placed in there-necked flask, add a certain amount of concentrated sulfuric acid and red fuming nitric acid (RFNA), the mass ratio that makes both is 4:1, and the gross mass of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 60 times of carbon nano-tube, ultrasonic dispersion 0.2h, the 0.5h that refluxes in the oil bath of 150 ℃ with the solution distilled water diluting, removes the upper strata stillness of night, repeatedly rinse for several times, be the polyethylene microporous membrane suction filtration of 0.2 μ m with the aperture, be washed to neutrality, obtain the carbon nano-tube of acidifying after vacuumize.
the preparation of graphene/carbon nanometer tube composite materials: take appropriate graphene oxide and the carbon nano-tube after acidification, the quality percentage composition that makes Graphene in the graphene/carbon nanometer tube composite materials is 0.01%, adding mass content is the deionized water of 300 times of carbon nano-tube gross masses after graphene oxide and acidifying, ultrasonic 1h, rapid stirring 0.2h, adding mass content is the sodium borohydride of 20 times of carbon nano-tube gross masses after graphene oxide and acidifying, continue to stir and make it to react 48h, it is the polyethylene microporous membrane suction filtration of 0.2 μ m with the aperture, washing, obtain the graphene/carbon nanometer tube composite materials after dry.
Lithium titanate is the preparation of composite negative pole material: lithium formate, isopropyl titanate, metatitanic acid methyl esters, tartaric acid and citric acid are dissolved in rapid stirring in appropriate solvent until form homogeneous solution A, wherein, the molar concentration of lithium ion is 0.01mol/L, the mol ratio of lithium and titanium is 3:5, and the mol ratio of titanium and glacial acetic acid is 1:0.05.Dropwise add the aqueous solution of the chromium chloride of 0.01mol/L in the solution A, the quality that makes the chromium element is that lithium titanate is 0.01% of composite negative pole material gross mass, and rapid stirring 0.2h gets solution B.The ethanolic solution that adds the graphene/carbon nanometer tube composite materials of 12g/L in the solution B, the gross mass that makes the graphene/carbon nanometer tube composite materials is that lithium titanate is 16.0% of composite negative pole material gross mass, continue to stir 6h and ultrasonic processing 0.2h, then continue rapid stirring until obtain Gel Precursor at 140 ℃, refinement after this Gel Precursor drying is obtained precursor powder, then with this powder in argon gas through 400 ℃ of calcining 48h, obtaining lithium titanate after refinement is composite negative pole material.
Being composite negative pole material with above-mentioned lithium titanate prepares button cell according to the method for embodiment 1, carries out charge-discharge test after will this button cell placing 24h in the voltage range of 1～2.5V, and its first discharge specific capacity is 160.7mAh/g under the multiplying power of 1C.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention is to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a lithium titanate is composite negative pole material, comprising: lithium titanate, doped chemical and graphene/carbon nanometer tube composite materials.
2. lithium titanate as claimed in claim 1 is composite negative pole material, it is characterized in that, described lithium titanate is that composite negative pole material is comprised of lithium titanate, doped chemical and graphene/carbon nanometer tube composite materials.
3. lithium titanate as claimed in claim 1 or 2 is composite negative pole material, it is characterized in that, described lithium titanate is that described lithium titanate is 80.0 ~ 99.8% of composite negative pole material quality, more preferably 85.0 ~ 99.8%, be particularly preferably 88.0 ~ 99.8%;
Preferably, described doped chemical is that described lithium titanate is 0.01 ~ 5.0% of composite negative pole material quality, more preferably 0.01 ~ 3.0%, be particularly preferably 0.01 ~ 2.0%;
Preferably, described graphene/carbon nanometer tube composite materials is that described lithium titanate is 0.01 ~ 16.0% of composite negative pole material quality, more preferably 0.01 ~ 12.0%, be particularly preferably 0.01 ~ 10.0%;
Preferably, described doped chemical is a kind or the combination of at least 2 kinds in Ru, Co, La, Mg, Zr, Ni, Mn, Y, Ag, Ca, Nb, Sr, V, Zn, Ta, Sn, Cr, Al, Ga or Cu;
Preferably, described Graphene accounts for 0.01 ~ 70.0% of graphene/carbon nanometer tube composite materials gross mass, and more preferably 0.01 ~ 60.0%, be particularly preferably 0.01 ~ 50.0%.
4. one kind is the preparation method of composite negative pole material as the described lithium titanate of claim 1-3 any one, comprises the following steps:
(1) lithium source, titanium source, chelating agent and doped chemical source are dispersed in medium, obtain mixed dispersion liquid;
(2) mixed dispersion liquid that step (1) is obtained is mixed with graphene/carbon nanometer tube composite materials dispersion liquid, obtains Gel Precursor;
(3) Gel Precursor that step (2) is obtained is dry, and then 400 ~ 1100 ℃ of calcinings, obtaining lithium titanate is composite negative pole material.
5. method as claimed in claim 4, is characterized in that, described step (1) comprising: lithium source, titanium source and chelating agent are dispersed in obtain dispersion liquid A in solvent, dispersion liquid A is mixed with doped chemical source dispersion liquid, obtain mixed dispersion liquid;
Preferably, described dispersion is under agitation carried out;
Preferably, described being mixed into dropwise is added to dispersion liquid A in the dispersion liquid of doped chemical source, and stirs at least 0.2 hour, and more preferably 0.3 ~ 1 hour, particularly preferably 0.5 hour;
Preferably, the concentration of lithium in dispersion liquid A is 0.01 ~ 3.0mol/L, and more preferably 0.05 ~ 2.0mol/L, be particularly preferably 0.1 ~ 1.0mol/L;
Preferably, described doped chemical source dispersion liquid is the aqueous solution in doped chemical source;
Preferably, in the dispersion liquid of described doped chemical source, the concentration in doped chemical source is 0.01～1mol/L, and more preferably 0.01～0.7mol/L, be particularly preferably 0.01～0.5mol/L;
Preferably, described solvent is water and/or organic solvent, more preferably water, ethanol, ethylene glycol, normal propyl alcohol, isopropyl alcohol, glycerol, acetone, methylethylketone, CCl
4Or a kind or the combination of at least 2 kinds in toluene, be particularly preferably a kind or the combination of at least 2 kinds in deionized water, acetone, ethanol or isopropyl alcohol.
6. method as described in claim 4 or 5, is characterized in that, step (2) comprising: add graphene/carbon nanometer tube composite materials dispersion liquid in the mixed dispersion liquid that step (1) obtains, the first stirring, ultrasonic processing is afterwards stirred again, obtains Gel Precursor;
Preferably, described first mixing time is at least 0.5 hour, more preferably 0.8 ~ 5 hour, is particularly preferably 1 hour;
Preferably, the described ultrasonic processing time is at least 0.2 hour, more preferably 0.3 ~ 5 hour, is particularly preferably 0.5 ~ 1 hour;
Preferably, described again being stirred under 50 ~ 140 ℃ carried out, and more preferably 60 ~ 130 ℃, is particularly preferably 80 ~ 120 ℃;
Preferably, the mol ratio of the described lithium of step (1) and titanium is 3:5 ~ 10:5, and more preferably 4:5 ~ 6:5, be particularly preferably 4:5;
Preferably, the mol ratio of the described titanium of step (1) and chelating agent is 1:0.05 ~ 1:1, and more preferably 1:0.08 ~ 1:0.7, be particularly preferably 1:0.1 ~ 1:0.5;
Preferably, described dispersion is dissolving independently.
7. as the described method of claim 4-6 any one, it is characterized in that, described titanium source is a kind or the combination of at least 2 kinds in butyl titanate, isopropyl titanate, titanium tetrachloride, titanyl sulfate, metatitanic acid methyl esters or iso-butyl titanate;
Preferably, described lithium source is a kind or the combination of at least 2 kinds in lithium dihydrogen phosphate, lithium carbonate, lithium acetate, lithium formate, lithium citrate, lithium chloride, lithium nitrate, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium oxalate, lithium sulfate, is particularly preferably a kind or the combination of at least 2 kinds in lithium acetate, lithium hydroxide, lithium nitrate, lithium chloride or lithium sulfate;
Preferably, described doped chemical source is the soluble-salt of doped chemical, is particularly preferably doped chemical nitrate and/or doped chemical acetate;
Preferably, described chelating agent is a kind or the combination of at least 2 kinds in glacial acetic acid, tartaric acid, oxalic acid, citric acid or acrylic acid, is particularly preferably citric acid;
Preferably, the described graphene/carbon nanometer tube composite materials of step (2) dispersion liquid is the ethanolic solution of graphene/carbon nanometer tube composite materials;
Preferably, in the described graphene/carbon nanometer tube composite materials of step (2) dispersion liquid, the concentration of graphene/carbon nanometer tube composite materials is 0.01～12g/L, and more preferably 0.05～10g/L, be particularly preferably 0.1～6g/L;
Preferably, carry out refinement before the described calcining of step (3);
Preferably, carry out refinement after the described calcining of step (3);
Preferably, the described calcining of step (3) is carried out under inert atmosphere; Described inert atmosphere is particularly preferably nitrogen and/or argon gas;
Preferably, the described calcining heat of step (3) is 450 ~ 1000 ℃, is particularly preferably 500 ~ 950 ℃;
Preferably, the described calcination time of step (3) is at least 1 hour, more preferably 2 ~ 48 hours, is particularly preferably 3 ~ 24 hours.
8. as the described method of claim 4-7 any one, it is characterized in that, the preparation method of described graphene/carbon nanometer tube composite materials comprises the following steps:
A) carbon nano-tube acidifying;
B) with the carbon nano-tube after graphene oxide, acidifying and solvent, then with the reducing agent reaction, removal of impurities obtains the graphene/carbon nanometer tube composite materials.
9. method as claimed in claim 8, it is characterized in that, described step a) comprises: the mixed acid that carbon nano-tube is placed in the concentrated sulfuric acid and red fuming nitric acid (RFNA), wherein, the mass ratio of mixed acid and carbon nano-tube is more than 20:1, and the mass ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 2:1 ~ 4:1, then disperse, 90 ~ 150 ℃ of reactions, last removal of impurities obtains the carbon nano-tube after acidifying; Preferably, the mass ratio of described mixed acid and carbon nano-tube is 30:1 ~ 60:1, is particularly preferably 40:1; Preferably, the mass ratio of the described concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3:1; Preferably, describedly be separated into ultrasonic dispersion; Preferably, described jitter time is 0.2 ~ 3 hour, more preferably 0.3 ~ 2 hour, is particularly preferably 0.5 ~ 1 hour; Preferably, described reaction temperature is 95 ~ 140 ℃, is particularly preferably 100 ~ 130 ℃; Preferably, the described reaction time is at least 0.5 hour, more preferably 0.8 ~ 5 hour, is particularly preferably 1 ~ 2 hour; Preferably, described removal of impurities comprises: solution distilled water diluting after reacting, remove the upper strata stillness of night, and repeatedly rinse for several times, be the polyethylene microporous membrane suction filtration of 0.2 μ m with the aperture, be washed to neutrality, last vacuumize;
Preferably, the described solvent of step b) is water and/or organic solvent, is particularly preferably deionized water;
Preferably, the gross mass of the carbon nano-tube after step b) graphene oxide and acidifying and the mass ratio of described solvent are below 1:100, and more preferably 1:300 ~ 1:100, be particularly preferably 1:200;
Preferably, the described mixing of step b) comprises ultrasonic and stirring successively; Preferably, described ultrasonic time is at least 0.2 hour, more preferably 0.3 ~ 1 hour, is particularly preferably 0.5 hour; Preferably, described mixing time is at least 0.2 hour, more preferably 0.3 ~ 1 hour, is particularly preferably 0.5 hour;
Preferably, the described reducing agent of step b) is a kind or the combination of at least 2 kinds in hydrazine, phenylhydrazine, ascorbic acid, sodium borohydride, p-phenylenediamine (PPD), ammoniacal liquor, Cys, glutathione or vitamin C, more preferably a kind in hydrazine, phenylhydrazine, sodium borohydride or p-phenylenediamine (PPD) or the combination of at least 2 kinds, be particularly preferably hydrazine;
Preferably, the gross mass of the carbon nano-tube after step b) graphene oxide and acidifying and the mass ratio of described reducing agent are below 1:5, and more preferably 1:8 ~ 1:20, be particularly preferably 1:10;
Preferably, the described reaction of step b) is under agitation carried out;
Preferably, the described reaction time of step b) is at least 10 hours, more preferably 12 ~ 48 hours, is particularly preferably 15 ~ 30 hours;
Preferably, the described removal of impurities of step b) comprises: be the polyethylene microporous membrane suction filtration of 0.2 μ m with the aperture, and washing, final drying.
10. as the described method of claim 4-9 any one, it is characterized in that, described lithium titanate is that the preparation method of composite negative pole material comprises the following steps:
(1) lithium source, titanium source and chelating agent are dispersed in obtain dispersion liquid A in solvent, wherein, the concentration of lithium is 0.01 ~ 3.0mol/L, and the mol ratio of lithium and titanium is 3:5 ~ 10:5, and the mol ratio of titanium and chelating agent is 1:0.05 ~ 1:1; Dispersion liquid A dropwise is added in the doped chemical source dispersion liquid of 0.01～1mol/L, mixes, obtain mixed dispersion liquid;
(2) mixed dispersion liquid that step (1) is obtained is mixed with the ethanolic solution of the graphene/carbon nanometer tube composite materials of 0.01～12g/L, stirs successively and ultrasonic processing, then continues to stir until obtain Gel Precursor at 50 ~ 140 ℃;
(3) after the Gel Precursor drying that step (2) is obtained, refinement obtains precursor powder, then in inert gas through 400 ~ 1100 ℃ of calcinings at least 1 hour, obtaining lithium titanate after refinement is composite negative pole material.
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