CN103151505B - A kind of Lithium-titanate composite negative pole and preparation method thereof - Google Patents
A kind of Lithium-titanate composite negative pole and preparation method thereof Download PDFInfo
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- CN103151505B CN103151505B CN201310065143.6A CN201310065143A CN103151505B CN 103151505 B CN103151505 B CN 103151505B CN 201310065143 A CN201310065143 A CN 201310065143A CN 103151505 B CN103151505 B CN 103151505B
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Abstract
The present invention relates to a kind of Lithium-titanate composite negative pole and preparation method thereof, the Lithium-titanate composite negative pole provided comprises lithium titanate, doped chemical and Graphene/carbon nanotube composite material.The soluble compound of titanium source, lithium source, doped chemical and Graphene/carbon nanotube composite material are obtained presoma by sol-gel in-situ synthesis, then this presoma is obtained Lithium-titanate composite negative pole through 400 ~ 1100 DEG C of calcinings.The present invention effectively improves lithium titanate anode material electron conduction and high rate performance by Graphene/carbon nanotube composite material, and the introducing of doped chemical effectively improves chemical property and the cyclical stability of lithium titanate anode material.Lithium-titanate composite negative pole prepared by the present invention has broad application prospects in field of lithium ion battery.
Description
Technical field
The present invention relates to lithium ion battery and supercapacitor technologies field, particularly, the present invention relates to a kind of Lithium-titanate composite negative pole 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 is mostly lithium intercalated graphite material with carbon element, but there are some problems in actual applications in this kind of material, as, first charge-discharge efficiency is lower, charge and discharge process volume changes, and easily forms Li dendrite and causes short circuit, make electrolyte decomposition there is potential safety hazard etc.By contrast, there is the lithium titanate of spinel structure, its theoretical capacity is 175mAh/g, in charge and discharge process, lithium ion insertion and deintercalation almost do not affect material structure, and be called " zero strain " material, charge and discharge platform is good and platform capacity can reach more than 90% of discharge capacity, good cycle, do not react with electrolyte, preparation method is simple, and cost is lower.Therefore, current spinel type lithium titanate has become the extremely wide lithium ion battery negative material of commercial applications prospect with the security feature of its excellence and long circulation life.
Although lithium titanate has many outstanding advantages as lithium ion battery negative material, and the electrochemical diffusion coefficient of lithium ion is 2 × 10 at normal temperatures
-8cm
2/ s, an order of magnitude larger than Carbon anode, but its intrinsic conductivity is lower, is only 10
-9s/cm, belongs to typical insulator, poorly conductive, thus when causing high power charging-discharging, poor-performing and special capacity fade are very fast, and heavy-current discharge performance is undesirable.The electric conductivity of material can be improved, to obtain good fast charging and discharging performance and cycle performance by doping.Chinese invention patent " a kind of lithium titanate anode material extremely preparation method of yttrium modification " (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 extremely preparation method of the lanthanum that adulterates " (CN102637864A), this patent adopts solid phase method to prepare the lithium titanate anode material of La doped, by the Trace La refinement crystal grain that adulterates, improve the chemical property of lithium titanate.The mode of above-mentioned two kinds of single metal ions of doping all achieves useful effect, but it is uneven thus affect the problem of chemical property to adopt solid phase method easily to produce raw material mixing when preparing.Chinese invention patent " preparation method of a kind of three-dimensional porous Graphene doping and coated lithium titanate composite anode material " (CN102646810A), disclose a kind of three-dimensional porous Graphene doping and the preparation method of coated lithium titanate composite material, effectively improved the high magnification chemical property of lithium titanate anode material by doping carbon material.But the three-dimensional porous grapheme material described in this patent is by hydro thermal method process, and still effectively can not suppress the stacking and agglomeration perhaps in sintering process of the lamella of Graphene, this limits the performance of its performance to a certain extent.
Therefore, develop a kind of preparation method simple, excellent electric conductivity, excellent electrochemical performance under high magnification, the lithium titanate system negative material with good electrochemical cycle stability is an affiliated art difficult problem.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of Lithium-titanate composite negative pole, and it has good electronics and lithium ion conductive, and excellent electrochemical performance under high magnification has good electrochemical cycle stability.
Described Lithium-titanate composite negative pole comprises: lithium titanate, doped chemical and Graphene/carbon nanotube composite material.
In the present invention, if no special instructions, "/" refers to " with ", such as described " Graphene/carbon nanotube composite material " refers to the composite material of Graphene and carbon nano-tube composition.
The preparation method of described Graphene/carbon nanotube composite material can be any prior art, such as, simply mix, and other method also can be adopted to prepare, and one of ordinary skill in the art can select as required.
Preferably, described Lithium-titanate composite negative pole is made up of lithium titanate, doped chemical and Graphene/carbon nanotube composite material.
Preferably, described lithium titanate is 80.0 ~ 99.8% of described Lithium-titanate composite negative pole 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 0.01 ~ 5.0% of described Lithium-titanate composite negative pole 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 nanotube composite material is 0.01 ~ 16.0% of described Lithium-titanate composite negative pole 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 composite negative pole comprises: lithium titanate, doped chemical and Graphene/carbon nanotube composite material, wherein, described lithium titanate is 80.0 ~ 99.8% of described Lithium-titanate composite negative pole quality, described doped chemical is 0.01 ~ 5.0% of described Lithium-titanate composite negative pole quality, and described Graphene/carbon nanotube composite material is 0.01 ~ 16.0% of described Lithium-titanate composite negative pole quality.
In another embodiment, described Lithium-titanate composite negative pole is made up of lithium titanate, doped chemical and Graphene/carbon nanotube composite material, wherein, described lithium titanate is 80.0 ~ 99.8% of described Lithium-titanate composite negative pole quality, described doped chemical is 0.01 ~ 5.0% of described Lithium-titanate composite negative pole quality, and described Graphene/carbon nanotube composite material is 0.01 ~ 16.0% of described Lithium-titanate composite negative pole quality.
Preferably, described doped chemical is the combination of in Ru, Co, La, Mg, Zr, Ni, Mn, Y, Ag, Ca, Nb, Sr, V, Zn, Ta, Sn, Cr, Al, Ga or Cu a kind or at least 2 kinds, 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 etc. of Ta, Sn, Cr, Al, Ga and Cu.
Preferably, described Graphene accounts for 0.01 ~ 70.0% of Graphene/carbon nanotube composite material 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%.
An object of the present invention is also the preparation method providing a kind of described Lithium-titanate composite negative pole, and described method is the in-situ doped method of sol-gel.
The preparation method of described Lithium-titanate composite negative pole comprises the following steps:
(1) by lithium source, titanium source, chelating agent and the dispersion of doped chemical source in media as well, mixed dispersion liquid is obtained;
(2) mixed dispersion liquid that step (1) obtains is mixed with Graphene/carbon nanotube composite material dispersion liquid, obtain Gel Precursor;
(3) Gel Precursor step (2) obtained is dry, then 400 ~ 1100 DEG C of calcinings, obtains Lithium-titanate composite negative pole.
Preferably, described step (1) comprising: lithium source, titanium source and chelating agent dispersion are obtained dispersion liquid A in a solvent, is mixed by dispersion liquid A, obtain mixed dispersion liquid with doped chemical source dispersion liquid; Preferably, described dispersion is under agitation carried out; Preferably, described in be mixed into dispersion liquid A be dropwise added in the dispersion liquid of doped chemical source, and to stir at least 0.2 hour, 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, more preferably 0.05 ~ 2.0mol/L, is 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, is 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 the combination of in toluene a kind or at least 2 kinds, 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 the combination etc. of toluene, be particularly preferably the combination of in deionized water, acetone, ethanol or isopropyl alcohol a kind or at least 2 kinds.
Preferably, step (2) comprising: in the mixed dispersion liquid that step (1) obtains, add Graphene/carbon nanotube composite material dispersion liquid, stir for the first time, ultrasonic process, stirs again afterwards, 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, described sonication treatment time is at least 0.2 hour, more preferably 0.3 ~ 5 hour, is particularly preferably 0.5 ~ 1 hour; Preferably, described be again stirred in 50 ~ 140 DEG C at carry out, more preferably 60 ~ 130 DEG C, be particularly preferably 80 ~ 120 DEG C.
Preferably, the mol ratio of step (1) described lithium and titanium is 3:5 ~ 10:5, more preferably 4:5 ~ 6:5, is particularly preferably 4:5.
Preferably, the mol ratio of step (1) described titanium and chelating agent is 1:0.05 ~ 1:1, more preferably 1:0.08 ~ 1:0.7, is particularly preferably 1:0.1 ~ 1:0.5.
Preferably, described dispersion is independently for dissolving.
Preferably, described titanium source is butyl titanate, isopropyl titanate, titanium tetrachloride, titanyl sulfate, 1 kind in metatitanic acid methyl esters or iso-butyl titanate or the combination of at least 2 kinds, 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 etc. of metatitanic acid methyl esters and iso-butyl titanate.
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 lithium, lithium oxalate, 1 kind in lithium sulfate or the combination of at least 2 kinds, 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 lithium, lithium phosphate, phosphoric acid hydrogen two lithium, 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 lithium, lithium chloride, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, the combination etc. of lithium phosphate and phosphoric acid hydrogen two lithium, is particularly preferably lithium acetate, lithium hydroxide, lithium nitrate, 1 kind in lithium chloride or lithium sulfate or the combination of at least 2 kinds.
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 the combination of in glacial acetic acid, tartaric acid, oxalic acid, citric acid or acrylic acid a kind or at least 2 kinds, 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., be particularly preferably citric acid.
Preferably, the described Graphene/carbon nanotube composite material dispersion liquid of step (2) is the ethanolic solution of Graphene/carbon nanotube composite material.
Preferably, in the described Graphene/carbon nanotube composite material dispersion liquid of step (2), the concentration of Graphene/carbon nanotube composite material is 0.01 ~ 12g/L, more preferably 0.05 ~ 10g/L, is particularly preferably 0.1 ~ 6g/L.
Preferably, refinement is carried out before step (3) described calcining.
Preferably, refinement is carried out after step (3) described calcining.
Preferably, step (3) described calcining is carried out under an inert atmosphere; 1 kind in described inert atmosphere such as nitrogen, helium, neon, argon gas, Krypton or xenon or the combination of at least 2 kinds, the mixed atmosphere of such as helium and nitrogen, 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 atmosphere etc. of nitrogen, helium, neon, argon gas and Krypton, is particularly preferably nitrogen and/or argon gas.
Preferably, step (3) described calcining heat is 450 ~ 1000 DEG C, is particularly preferably 500 ~ 950 DEG C.
Preferably, step (3) described calcination time is at least 1 hour, more preferably 2 ~ 48 hours, is particularly preferably 3 ~ 24 hours.
Preferably, the preparation method of described Graphene/carbon nanotube composite material comprises the following steps:
A) carbon nano-tube acidifying;
B) by the carbon nano-tube after graphene oxide, acidifying and solvent, then react with reducing agent, removal of impurities, obtains Graphene/carbon nanotube composite material.
Described cabonic acid turns to prior art, and one of ordinary skill in the art can select as required.
Preferably, described step a) comprises: mixed acid carbon nano-tube being 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 DEG C 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, ultrasonic disperse is separated into described in; 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 DEG C, is particularly preferably 100 ~ 130 DEG C; 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, and removes supernatant, repeatedly rinses for several times, is the polyethylene microporous membrane suction filtration of 0.2 μm, is washed to neutrality, last vacuumize with aperture.
In the present invention, the described concentrated sulfuric acid refers to that mass fraction is more than or equal to the sulfuric acid solution of 70%; Described red fuming nitric acid (RFNA) refers to that mass fraction is more than or equal to the salpeter solution of 60%.
Preferably, solvent described in step b) is water and/or organic solvent, is particularly preferably deionized water.
Preferably, the gross mass of 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, is particularly preferably 1:200.
Preferably, described in step b), mixing comprises ultrasonic successively and stirs; 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, reducing agent described in step b) is the combination of in hydrazine, phenylhydrazine, ascorbic acid, sodium borohydride, p-phenylenediamine (PPD), ammoniacal liquor, Cys, glutathione or vitamin C a kind or at least 2 kinds, 1 kind more preferably 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 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, is particularly preferably 1:10.
Preferably, react described in step b) and under agitation carry out.
Preferably, the reaction time described in step b) is at least 10 hours, more preferably 12 ~ 48 hours, is particularly preferably 15 ~ 30 hours.
Preferably, removal of impurities described in step b) comprises: the polyethylene microporous membrane suction filtration with aperture being 0.2 μm, washing, final drying.
Preferably, the preparation method of described Lithium-titanate composite negative pole comprises the following steps:
(1) lithium source, titanium source and chelating agent dispersion are obtained dispersion liquid A in a 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; Dropwise be added to by dispersion liquid A in the doped chemical source dispersion liquid of 0.01 ~ 1mol/L, mixing, obtains mixed dispersion liquid;
(2) mixed dispersion liquid that step (1) obtains is mixed with the ethanolic solution of the Graphene/carbon nanotube composite material of 0.01 ~ 12g/L, stir successively and ultrasonic process, then continue to stir until obtain Gel Precursor at 50 ~ 140 DEG C;
(3) after Gel Precursor drying step (2) obtained, refinement obtains precursor powder, then calcines at least 1 hour through 400 ~ 1100 DEG C in inert gas, obtains Lithium-titanate composite negative pole after refinement.
Adopt Lithium-titanate composite negative pole prepared by the method for the invention, doped chemical, lithium, titanium and graphene/carbon nano-tube complex carbon material mix, and make Lithium-titanate composite negative pole have excellent chemical property.
Outstanding advantages of the present invention and good effect as follows:
(1) the present invention adopts the in-situ doped legal system of sol-gel for the Lithium-titanate composite negative pole of metallic element and the modification of graphene/carbon nano-tube complex carbon material co-doped, compared with adulterating with solid phase method, in preparation process, the soluble compound of metallic element, lithium source and titanium source can reach the Homogeneous phase mixing of molecular level, effectively can 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 doped with graphene/carbon nano-tube complex carbon material in the process of preparation Lithium-titanate composite negative pole, this complex carbon material serves the effect of electric transmission resilient coating in negative material, the lithium ion diffusion coefficient of lithium titanate composite anode material can be increased, its cycle performance of effective raising, this negative material is made electrode diaphragm and and metal lithium sheet be assembled into battery, find afterwards after tested, the capability retention after 50 times that circulates under 0.5C multiplying power is greater than 98%.
(3) in the graphene/carbon nano-tube complex carbon material provided in the present invention, Graphene is kept apart by carbon nano-tube is well-proportioned, effectively prevent Graphene after the drying and with the lamination in lithium titanate recombination process and agglomeration, increased substantially the chemical property of Lithium-titanate composite negative pole.
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 is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
The method of testing of Lithium-titanate composite negative pole prepared by following examples is as follows:
After the Lithium-titanate composite negative pole of preparation, acetylene black and Kynoar are weighed according to the mass ratio of 95:5:5, uniform sizing material is mixed with by the mode of ultrasonic disperse and rapid stirring and 1-METHYLPYRROLIDONE, be coated in after froth in vacuum in current collector aluminum foil, flatten on roll squeezer after 80 DEG C of dryings and make electrode diaphragm, this diaphragm is washed into the disk that diameter is 9mm, it is assembled into button cell with lithium sheet after 120 DEG C of vacuumize 12h, and electrolyte adopts the LiPF containing 1mol/L
6ethyl carbonate and the mixed liquor of dimethyl carbonate (volume ratio 1:1).In the voltage range of 1 ~ 2.5V, carry out charge-discharge test after this button cell is placed 24h, under the multiplying power of 1C, its first discharge specific capacity is greater than 158mAh/g.
Embodiment 1
Carbon nano-tube acidifying: weigh appropriate carbon nano-tube and be placed in there-necked flask, add a certain amount of concentrated sulfuric acid and red fuming nitric acid (RFNA), make both mass ratioes be 3:1, the gross mass of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 40 times of carbon nano-tube, ultrasonic disperse 0.5h, reflux 2h in the oil bath of 100 DEG C, by solution distilled water diluting, removes supernatant, repeatedly rinse for several times, with the polyethylene microporous membrane suction filtration that aperture is 0.2 μm, be washed to neutrality, after vacuumize, obtain the carbon nano-tube of acidifying.
The preparation of Graphene/carbon nanotube composite material: take the carbon nano-tube after appropriate graphene oxide and acidification, the mass percentage of Graphene in Graphene/carbon nanotube composite material is made to be 0.01%, add the deionized water that mass content is the carbon nano-tube gross mass 200 times after graphene oxide and acidifying, ultrasonic 0.5h, rapid stirring 0.5h, add the hydrazine that mass content is the carbon nano-tube gross mass 10 times after graphene oxide and acidifying, continue stirring to make it to react 30h, with the polyethylene microporous membrane suction filtration that aperture is 0.2 μm, washing, Graphene/carbon nanotube composite material is obtained after drying.
The preparation of Lithium-titanate composite negative pole: 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.In solution A, dropwise add total concentration is the lanthanum nitrate of 0.5mol/L and the aqueous solution of strontium nitrate, and make the gross mass of lanthanum and strontium element be 2.0% of Lithium-titanate composite negative pole gross mass, rapid stirring 0.5h obtains solution B.The ethanolic solution of the Graphene/carbon nanotube composite material of 6g/L is added in solution B, the gross mass of Graphene/carbon nanotube composite material is made to be 10.0% of Lithium-titanate composite negative pole gross mass, continue to stir 1h and ultrasonic process 0.5h, then rapid stirring is continued until obtain Gel Precursor at 120 DEG C, refinement after this Gel Precursor drying is obtained precursor powder, then by this powder in the mist of nitrogen and argon gas through 950 DEG C of calcining 3h, obtain Lithium-titanate composite negative pole after refinement.
Uniform sizing material is mixed with by the mode of ultrasonic disperse and rapid stirring and 1-METHYLPYRROLIDONE after above-mentioned Lithium-titanate composite negative pole, acetylene black and Kynoar being weighed according to the mass ratio of 95:5:5, be coated in after froth in vacuum in current collector aluminum foil, flatten on roll squeezer after 80 DEG C of dryings and make electrode diaphragm, this diaphragm is washed into the disk that diameter is 9mm, it is assembled into button cell with lithium sheet after 120 DEG C of vacuumize 12h, and electrolyte adopts the LiPF containing 1mol/L
6ethyl carbonate and the mixed liquor of dimethyl carbonate (volume ratio 1:1).In the voltage range of 1 ~ 2.5V, carry out charge-discharge test after this button cell is placed 24h, under the multiplying power of 1C, its first discharge specific capacity is 171.5mAh/g.
Embodiment 2
First by carbon nano-tube acidifying, method is with embodiment 1, unlike 1h ultrasonic in acidization, reflux 1h in the oil bath of 130 DEG C, then Graphene/carbon nanotube composite material is prepared, method is with embodiment 1, and the mass percentage unlike Graphene in Graphene/carbon nanotube composite material is 50%, reacts 26h after adding hydrazine.
The preparation of Lithium-titanate composite negative pole: 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.In solution A, dropwise add total concentration is the calcium nitrate of 0.01mol/L and the aqueous solution of nickel nitrate, and make the gross mass of calcium and nickel element be 1.0% of Lithium-titanate composite negative pole gross mass, rapid stirring 0.5h obtains solution B.The ethanolic solution of the Graphene/carbon nanotube composite material of 0.1g/L is added in solution B, the gross mass of Graphene/carbon nanotube composite material is made to be 0.01% of Lithium-titanate composite negative pole gross mass, continue to stir 1h and ultrasonic process 1h, then rapid stirring is continued until obtain Gel Precursor at 80 DEG C, refinement after this Gel Precursor drying is obtained precursor powder, then this powder is calcined 24h through 500 DEG C in nitrogen, after refinement, obtain Lithium-titanate composite negative pole.
Above-mentioned Lithium-titanate composite negative pole is prepared button cell according to the method for embodiment 1, and in the voltage range of 1 ~ 2.5V, carry out charge-discharge test after this button cell is placed 24h, under the multiplying power of 1C, its first discharge specific capacity is 171.5mAh/g.
Embodiment 3
First by carbon nano-tube acidifying, method is with embodiment 1, unlike 0.6h ultrasonic in acidization, reflux 1.5h in the oil bath of 120 DEG C, then Graphene/carbon nanotube composite material is prepared, method is with embodiment 1, and the mass percentage unlike Graphene in Graphene/carbon nanotube composite material is 20%, reacts 20h after adding hydrazine.
The preparation of Lithium-titanate composite negative pole: 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.In solution A, dropwise add the aqueous solution of 0.1mol/L ruthenic chloride, make the quality of ruthenium element be 0.5% of Lithium-titanate composite negative pole gross mass, rapid stirring 0.5h obtains solution B.The ethanolic solution of the Graphene/carbon nanotube composite material of 1.0g/L is added in solution B, the gross mass of Graphene/carbon nanotube composite material is made to be 3.0% of Lithium-titanate composite negative pole gross mass, continue to stir 1h and ultrasonic process 1h, then rapid stirring is continued until obtain Gel Precursor at 100 DEG C, refinement after this Gel Precursor drying is obtained precursor powder, then this powder is calcined 20h through 650 DEG C in argon gas, after refinement, obtain Lithium-titanate composite negative pole.
Above-mentioned Lithium-titanate composite negative pole is prepared button cell according to the method for embodiment 1, and in the voltage range of 1 ~ 2.5V, carry out charge-discharge test after this button cell is placed 24h, under the multiplying power of 1C, its first discharge specific capacity is 163.2mAh/g.
Embodiment 4
First by carbon nano-tube acidifying, method, with embodiment 1, then prepares Graphene/carbon nanotube composite material, and method is with embodiment 1, and the mass percentage unlike Graphene in Graphene/carbon nanotube composite material is 35%, reacts 24h after adding hydrazine.
The preparation of Lithium-titanate composite negative pole: 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.In solution A, dropwise add total concentration is the cobalt acetate of 0.3mol/L and the aqueous solution of magnesium acetate, and make the gross mass of cobalt and magnesium elements be 1.5% of Lithium-titanate composite negative pole gross mass, rapid stirring 0.5h obtains solution B.The ethanolic solution of the Graphene/carbon nanotube composite material of 3.0g/L is added in solution B, the gross mass of Graphene/carbon nanotube composite material is made to be 7.0% of Lithium-titanate composite negative pole gross mass, continue to stir 1h and ultrasonic process 1h, then rapid stirring is continued until obtain Gel Precursor at 110 DEG C, refinement after this Gel Precursor drying is obtained precursor powder, then this powder is calcined 15h through 800 DEG C in argon gas, after refinement, obtain Lithium-titanate composite negative pole.
Above-mentioned Lithium-titanate composite negative pole is prepared button cell according to the method for embodiment 1, and in the voltage range of 1 ~ 2.5V, carry out charge-discharge test after this button cell is placed 24h, under the multiplying power of 1C, its first discharge specific capacity is 168.6mAh/g.
Embodiment 5
Carbon nano-tube acidifying: weigh appropriate carbon nano-tube and be placed in there-necked flask, add a certain amount of concentrated sulfuric acid and red fuming nitric acid (RFNA), make both mass ratioes be 2:1, the gross mass of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 20 times of carbon nano-tube, ultrasonic disperse 3h, reflux 6h in the oil bath of 90 DEG C, by solution distilled water diluting, removes supernatant, repeatedly rinse for several times, with the polyethylene microporous membrane suction filtration that aperture is 0.2 μm, be washed to neutrality, after vacuumize, obtain the carbon nano-tube of acidifying.
The preparation of Graphene/carbon nanotube composite material: take the carbon nano-tube after appropriate graphene oxide and acidification, the mass percentage of Graphene in Graphene/carbon nanotube composite material is made to be 70.0%, add the deionized water that mass content is the carbon nano-tube gross mass 100 times after graphene oxide and acidifying, ultrasonic 0.2h, rapid stirring 1h, add the p-phenylenediamine (PPD) that mass content is the carbon nano-tube gross mass 5 times after graphene oxide and acidifying, continue stirring to make it to react 10h, with the polyethylene microporous membrane suction filtration that aperture is 0.2 μm, washing, Graphene/carbon nanotube composite material is obtained after drying.
The preparation of Lithium-titanate composite negative pole: by tert-butyl alcohol lithium, lithium acetate, titanyl sulfate, citric acid and dissolving oxalic acid in appropriate solvent rapid stirring 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.In solution A, dropwise add total concentration is the zinc chloride of 1mol/L and the aqueous solution of manganese chloride, and make the gross mass of zinc and manganese element be 5.0% of Lithium-titanate composite negative pole gross mass, rapid stirring 1h obtains solution B.The ethanolic solution of the Graphene/carbon nanotube composite material of 0.01g/L is added in solution B, the gross mass of Graphene/carbon nanotube composite material is made to be 0.01% of Lithium-titanate composite negative pole gross mass, continue to stir 0.5h and ultrasonic process 5h, then rapid stirring is continued until obtain Gel Precursor at 50 DEG C, refinement after this Gel Precursor drying is obtained precursor powder, then this powder is calcined 1h through 1100 DEG C in helium, after refinement, obtain Lithium-titanate composite negative pole.
Above-mentioned Lithium-titanate composite negative pole is prepared button cell according to the method for embodiment 1, and in the voltage range of 1 ~ 2.5V, carry out charge-discharge test after this button cell is placed 24h, under the multiplying power of 1C, its first discharge specific capacity is 166.4mAh/g.
Embodiment 6
Carbon nano-tube acidifying: weigh appropriate carbon nano-tube and be placed in there-necked flask, add a certain amount of concentrated sulfuric acid and red fuming nitric acid (RFNA), make both mass ratioes be 4:1, the gross mass of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 60 times of carbon nano-tube, ultrasonic disperse 0.2h, reflux 0.5h in the oil bath of 150 DEG C, by solution distilled water diluting, removes supernatant, repeatedly rinse for several times, with the polyethylene microporous membrane suction filtration that aperture is 0.2 μm, be washed to neutrality, after vacuumize, obtain the carbon nano-tube of acidifying.
The preparation of Graphene/carbon nanotube composite material: take the carbon nano-tube after appropriate graphene oxide and acidification, the mass percentage of Graphene in Graphene/carbon nanotube composite material is made to be 0.01%, add the deionized water that mass content is the carbon nano-tube gross mass 300 times after graphene oxide and acidifying, ultrasonic 1h, rapid stirring 0.2h, add the sodium borohydride that mass content is the carbon nano-tube gross mass 20 times after graphene oxide and acidifying, continue stirring to make it to react 48h, with the polyethylene microporous membrane suction filtration that aperture is 0.2 μm, washing, Graphene/carbon nanotube composite material is obtained after drying.
The preparation of Lithium-titanate composite negative pole: 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.In solution A, dropwise add the aqueous solution of the chromium chloride of 0.01mol/L, make the quality of chromium element be 0.01% of Lithium-titanate composite negative pole gross mass, rapid stirring 0.2h obtains solution B.The ethanolic solution of the Graphene/carbon nanotube composite material of 12g/L is added in solution B, the gross mass of Graphene/carbon nanotube composite material is made to be 16.0% of Lithium-titanate composite negative pole gross mass, continue to stir 6h and ultrasonic process 0.2h, then rapid stirring is continued until obtain Gel Precursor at 140 DEG C, refinement after this Gel Precursor drying is obtained precursor powder, then this powder is calcined 48h through 400 DEG C in argon gas, after refinement, obtain Lithium-titanate composite negative pole.
Above-mentioned Lithium-titanate composite negative pole is prepared button cell according to the method for embodiment 1, and in the voltage range of 1 ~ 2.5V, carry out charge-discharge test after this button cell is placed 24h, under the multiplying power of 1C, its first discharge specific capacity is 160.7mAh/g.
Applicant states, 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, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (27)
1. a Lithium-titanate composite negative pole, is characterized in that, described Lithium-titanate composite negative pole is made up of lithium titanate, doped chemical and Graphene/carbon nanotube composite material; Wherein, described Graphene accounts for 0.01 ~ 50.0% of Graphene/carbon nanotube composite material gross mass; Described lithium titanate is 80.0 ~ 89.0% of described Lithium-titanate composite negative pole quality; Described doped chemical is 1.0 ~ 5.0% of described Lithium-titanate composite negative pole quality; Described Graphene/carbon nanotube composite material is 1 ~ 16.0% of described Lithium-titanate composite negative pole quality;
The preparation method of described Lithium-titanate composite negative pole, comprises the following steps:
(1) lithium source, titanium source and chelating agent dispersion are obtained dispersion liquid A in a solvent, dispersion liquid A is dropwise added in the aqueous solution in doped chemical source, and stirs at least 0.2 hour, obtain mixed dispersion liquid;
Wherein, described solvent is water, ethanol, ethylene glycol, normal propyl alcohol, isopropyl alcohol, glycerol, acetone, methylethylketone, CCl
4or the combination of in toluene a kind or at least 2 kinds; Described chelating agent is the combination of in glacial acetic acid, tartaric acid, oxalic acid, citric acid or acrylic acid a kind or at least 2 kinds;
The mol ratio of described lithium and titanium is 3:5 ~ 10:5; The mol ratio of described titanium and chelating agent is 1:0.05 ~ 1:1;
(2) mixed dispersion liquid that step (1) obtains is mixed with the ethanolic solution of Graphene/carbon nanotube composite material, obtain Gel Precursor;
(3) Gel Precursor step (2) obtained is dry, and then 400 ~ 1100 DEG C of calcinings at least 1 hour, wherein, described calcining is carried out under an inert atmosphere; Described inert atmosphere is nitrogen and/or argon gas, obtains Lithium-titanate composite negative pole.
2. Lithium-titanate composite negative pole as claimed in claim 1, it is characterized in that, described doped chemical is the combination of in Ru, Co, La, Mg, Zr, Ni, Mn, Y, Ag, Ca, Nb, Sr, V, Zn, Ta, Sn, Cr, Al, Ga or Cu a kind or at least 2 kinds.
3. Lithium-titanate composite negative pole as claimed in claim 1, it is characterized in that, the concentration of lithium in dispersion liquid A is 0.01 ~ 3.0mol/L.
4. Lithium-titanate composite negative pole as claimed in claim 1, it is characterized in that, in the aqueous solution in described doped chemical source, the concentration in doped chemical source is 0.01 ~ 1mol/L.
5. Lithium-titanate composite negative pole as claimed in claim 1, it is characterized in that, step (2) comprising: the ethanolic solution adding Graphene/carbon nanotube composite material in the mixed dispersion liquid that step (1) obtains, first stirring, ultrasonic process afterwards, again stir, obtain Gel Precursor.
6. Lithium-titanate composite negative pole as claimed in claim 5, it is characterized in that, the time of described first stirring is at least 0.5 hour.
7. Lithium-titanate composite negative pole as claimed in claim 5, it is characterized in that, the time of described ultrasonic process is at least 0.2 hour.
8. Lithium-titanate composite negative pole as claimed in claim 5, is characterized in that, described be again stirred in 50 ~ 140 DEG C at carry out.
9. Lithium-titanate composite negative pole as claimed in claim 1, is characterized in that, described dispersion is independently for dissolving.
10. Lithium-titanate composite negative pole as claimed in claim 1, is characterized in that, described titanium source is the combination of in butyl titanate, isopropyl titanate, titanium tetrachloride, titanyl sulfate, metatitanic acid methyl esters or iso-butyl titanate a kind or at least 2 kinds.
11. Lithium-titanate composite negative pole as claimed in claim 1, it is characterized in that, described lithium source is the combination of 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 lithium, lithium oxalate, lithium sulfate a kind or at least 2 kinds.
12. Lithium-titanate composite negative pole as claimed in claim 1, it is characterized in that, described doped chemical source is the soluble-salt of doped chemical.
13. Lithium-titanate composite negative pole as claimed in claim 1, it is characterized in that, in the ethanolic solution of step (2) described Graphene/carbon nanotube composite material, the concentration of Graphene/carbon nanotube composite material is 0.01 ~ 12g/L.
14. Lithium-titanate composite negative pole as claimed in claim 1, is characterized in that, carry out refinement before step (3) described calcining.
15. Lithium-titanate composite negative pole as claimed in claim 1, is characterized in that, carry out refinement after step (3) described calcining.
16. Lithium-titanate composite negative pole as claimed in claim 1, it is characterized in that, step (3) described calcining heat is 450 ~ 1000 DEG C.
17. Lithium-titanate composite negative pole as claimed in claim 1, it is characterized in that, the preparation method of described Graphene/carbon nanotube composite material comprises the following steps:
A) carbon nano-tube acidifying;
B) by the carbon nano-tube after graphene oxide, acidifying and solvent, then react with reducing agent, removal of impurities, obtains Graphene/carbon nanotube composite material.
18. Lithium-titanate composite negative pole as claimed in claim 17, it is characterized in that, described step a) comprising: mixed acid carbon nano-tube being 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 DEG C of reactions, last removal of impurities, obtains the carbon nano-tube after acidifying.
19. Lithium-titanate composite negative pole as claimed in claim 17, is characterized in that, step b) described solvent is water and/or organic solvent.
20. Lithium-titanate composite negative pole as claimed in claim 17, is characterized in that, step b) gross mass of carbon nano-tube after graphene oxide and acidifying and the mass ratio of described solvent be below 1:100.
21. Lithium-titanate composite negative pole as claimed in claim 17, is characterized in that, step b) described mixing comprises ultrasonic successively and stirs; Described ultrasonic time is at least 0.2 hour; Described mixing time is at least 0.2 hour.
22. Lithium-titanate composite negative pole as claimed in claim 17, it is characterized in that, step b) described reducing agent is the combination of in hydrazine, phenylhydrazine, ascorbic acid, sodium borohydride, p-phenylenediamine (PPD), ammoniacal liquor, Cys, glutathione or vitamin C a kind or at least 2 kinds.
23. Lithium-titanate composite negative pole as claimed in claim 17, is characterized in that, step b) gross mass of carbon nano-tube after graphene oxide and acidifying and the mass ratio of described reducing agent be below 1:5.
24. Lithium-titanate composite negative pole as claimed in claim 17, is characterized in that, step b) described reaction under agitation carries out.
25. Lithium-titanate composite negative pole as claimed in claim 17, is characterized in that, step b) the described reaction time is at least 10 hours.
26. Lithium-titanate composite negative pole as claimed in claim 17, is characterized in that, step b) described removal of impurities comprises: the polyethylene microporous membrane suction filtration with aperture being 0.2 μm, washing, final drying.
27. Lithium-titanate composite negative pole as claimed in claim 1, it is characterized in that, the preparation method of described Lithium-titanate composite negative pole comprises the following steps:
(1) lithium source, titanium source and chelating agent dispersion are obtained dispersion liquid A in a 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 is dropwise added in the aqueous solution in doped chemical source of 0.01 ~ 1mol/L, mixing, and stirs at least 0.2 hour, obtain mixed dispersion liquid;
Wherein, described solvent is water, ethanol, ethylene glycol, normal propyl alcohol, isopropyl alcohol, glycerol, acetone, methylethylketone, CCl
4or the combination of in toluene a kind or at least 2 kinds; Described chelating agent is the combination of in glacial acetic acid, tartaric acid, oxalic acid, citric acid or acrylic acid a kind or at least 2 kinds;
(2) mixed dispersion liquid that step (1) obtains is mixed with the ethanolic solution of the Graphene/carbon nanotube composite material of 0.01 ~ 12g/L, stir successively and ultrasonic process, then continue to stir until obtain Gel Precursor at 50 ~ 140 DEG C;
(3) after Gel Precursor drying step (2) obtained, refinement obtains precursor powder, then calcines at least 1 hour through 400 ~ 1100 DEG C in nitrogen and/or argon gas, obtains Lithium-titanate composite negative pole after refinement.
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