CN103771500A - Preparation method of lithium ion secondary battery with nanometer lithium titanate simultaneously doped at A and B site - Google Patents
Preparation method of lithium ion secondary battery with nanometer lithium titanate simultaneously doped at A and B site Download PDFInfo
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Abstract
The invention provides a preparation method of lithium ion secondary battery with nanometer lithium titanate simultaneously doped at A and B sites. By using sol-gel method, soluble compounds of Li and Ti are prepared according to a mol ratio Li/Ti=0.8-1.0, and the mixture is added into an alcohol-water mixed solvent mixed with a hydrolysis inhibitor, and a dual component chelating agent and metal ions are added, after stirring, heating and gelling, a sintered precursor is obtained; after ball milling and thermal insulation of the obtained precursor, Li4Ti5O12 with A and B site simultaneously doped is obtained. Li4Ti5O12 and carbon source are mixed in an aqueous solution containing emulsifier, finally, the uniform mixture of lithium titanate and carbon source is heated, and a Li4Ti5O12/C combined electrode with rare earth elements simultaneously doped at A and B site is obtained. The lithium titanate prepared by the method has good dispersion effect, uniform carbon coating and high conductivity. The initial discharge specific capacity of the Li4Ti5O12/C composite material prepared by the method at room temperature at 1C multiplying power reaches to 178 mAh/g, and the discharge specific capacity at 20C multiplying power still maintains about 110 mAh/g, so that the composite material has excellent multiplying power performance and circulating stability and can be widely applied in the fields of portable instrument and power battery.
Description
Technical field
The present invention relates to a kind of preparation method of lithium-ion secondary cell nanometer combined electrode material lithium titanate, particularly relate to the preparation method of the coated combination electrode material lithium titanate of carbon that a kind of rare earth ion A, B position adulterate simultaneously.
Background technology
The advantage such as lithium-ion secondary cell has that energy density is high, memory-less effect, self-discharge are little, occupies an leading position in energy-storage battery market, is widely used on the portable type electronic products such as notebook computer, mobile phone, PDA, digital camera.Along with the development of new technology and the exhaustion of fossil resource, such secondary energy storage battery is progressively applied in the energy-saving cleaning cart such as electric bicycle, electromobile field.In current existing battery system, lithium secondary battery is acknowledged as and can meets better one of power truck power cell to power stage, operating range, acceleration capacity, work-ing life and specific energy density requirement.At present, the negative material of business-like lithium ion battery adopts all kinds of carbon materials mostly, but it also exists some inevitable defects: when battery changes into, react form SEI film with electrolytic solution, cause the consumption of electrolytic solution and lower coulomb efficiency first; When over-charging of battery, may be at carbon electrodes precipitating metal lithium, form Li dendrite and cause short circuit, cause temperature to raise, battery explosion; In addition, the spread coefficient of lithium ion in carbon material is less, causes battery can not realize high current charge-discharge, thereby has limited the range of application of lithium ion battery.
Spinel type Li
4ti
5o
12as a kind of novel negative material, owing to thering is higher electropotential (~ 1.55V, with respect to metal Li), suppressed Li dendrite separates out on negative pole, solved the internal short-circuit problem of battery, thereby the security that has improved battery becomes current study hotspot.In addition Li,
4ti
5o
12be a kind of " zero strain " material, unit cell parameters changes hardly before and after lithium ion embeds and deviates from, thereby makes it have good cycle performance and sparking voltage stably.At normal temperatures, lithium ion exceeds an order of magnitude at the spread coefficient of electrode interior than on carbon negative pole material, can realize charge-discharge velocity faster simultaneously.In sum, Li
4ti
5o
12be one of candidate material of following alternative conventional carbon negative material, there is the value of further investigation.But, Li
4ti
5o
12specific conductivity very low, be close to insulation, the poor-performing under high magnification, will be subject to great restriction if be applied to the field such as power car, large-scale energy-storage battery.Thereby, for Li
4ti
5o
12the shortcoming of material poorly conductive, the research that improves its specific conductivity and high rate capability seems particularly important.At present, usually said ion doping is (Li position), B position (Ti position) or O position dopant ion in A position, improves the defect structure of lithium titanate, improves the specific conductivity of material itself, reduces the resistance of electrode materials, tentatively promotes electrode performance with this.
Rare earth metal doping can effectively improve the specific conductivity of lithium titanate, improve its fast charging and discharging performance and cyclical stability, if publication number is the patent of CN101456581A and CN101567442A, but they be all prepare with solid phase method and rare earth element be mostly directly doped to B position, particle agglomeration is more serious, can affect to a certain extent the performance of battery or can not bring into play to greatest extent thulium effect of improving specific conductivity.
Summary of the invention
The object of the invention is to overcome prior art and prepare the high magnification existing in lithium titanate anode material and transfer the defect of poor electrical performance, provide a kind of by simultaneously rare-earth metal doped and there is the method for the matrix material lithium titanate of excellent electrochemical performance in conjunction with the sol-gel method preparation of two-pack sequestrant in A, B position.The standby A of this legal system, the coated combination electrode material lithium titanate of carbon adulterating in B position are simultaneously shown mutually or the specific conductivity of body phase is all improved, and demonstrate excellent high rate performance and cycle performance.
For reaching above-mentioned expection object, the present invention adopts following technical scheme:
Lithium-ion secondary cell A, a B position preparation method for dopen Nano lithium titanate simultaneously, is characterized in that, comprises the steps:
A. ethanol and water are pressed to the volume ratio premix composition mixing solutions of 1:0～0.5, then add the inhibitor of acid as follow-up titanium (Ti) soluble compounds hydrolysis reaction, or the solvating agent of lithium (Li) slightly soluble compound;
B. by the slightly soluble of lithium and titanium or soluble compound, prepare burden according to the mol ratio of Li:Ti=0.8～1.0:1, join in the mixed solution that step a makes, by magnetic force heating stirrer stirring at normal temperature, until all dissolve;
C. by rare earth metal (RE) compound for lithium titanate A, the doping of B position, according to Li(or Ti): the mol ratio of RE=1:0.01～0.1 is prepared burden, join in the mixed solution that step b makes, by magnetic force heating stirrer stirring at normal temperature, until all dissolve;
D. by two-pack sequestrant with water premix, water and sequestrant volume ratio are 0.5～2:1, mix rear dropping ammoniacal liquor until sequestrant all dissolves, and then join in the mixed solution that step c makes, and add ammoniacal liquor to regulate pH value to 7～10, continuation stirring;
E. be stirred into after colloidal sol until the mixed solution of steps d, start heating, continue to stir simultaneously, Heating temperature is 60～100
oC, be 1～3 hour heat-up time, to gel state, then in the convection oven of 150 ℃～250 ℃, dries 3～24 hours, obtains the lithium titanate precursor of black;
F. lithium titanate precursor step e being made is put into high energy ball mill ball milling 1～10 hour, then puts into retort furnace and calcines 5～15 hours, obtains the nano barium titanate powder for lithium that rare earth element A, B position adulterate simultaneously; Wherein the rotating speed of ball milling is 300～550 r/min, and ball milling post-drying temperature is 60～200 ℃;
G. the nano lithium titanate of step f gained is directly mixed with carbon source in water, add OP series, or hexadecyl benzene sulfonic acid sodium salt is as emulsifying agent, the volume ratio of emulsifying agent and water is 0.01～0.2:1 simultaneously, after stirring 1～10 hour, start heating, temperature range is 60～100 ℃;
H. solid remaining after step g heating is taken out and ground, finally put into tubular type kiln roasting, pass into rare gas element, gas is chosen as the one in argon gas, nitrogen, helium, maturing temperature is 700 ℃～900 ℃, time is 5～20 hours, finally obtains A, the B position lithium-ion secondary cell combination electrode material Li of doped with rare-earth elements simultaneously
4ti
5o
12/ C.
The described acid of step (a) is a kind of or its combination in nitric acid, hydrochloric acid, acetic acid, tartrate, oxalic acid, oxysuccinic acid, citric acid, xitix, phenylformic acid, Whitfield's ointment, coffic acid, and alcohol and sour volume ratio are alcohol: acid=1:0.01～0.1.
Described slightly soluble or the soluble lithium compounds of step (b) is the one in lithium nitrate, Quilonum Retard, lithium chloride, Lithium Acetate, Lithium Citrate de, lithium oxalate, lithium formate, lithium lactate, isopropyl lithium alkoxide, long-chain or short-chain alkyl lithium.
The described soluble titanium compound of step (b) is tetra-n-butyl titanate, or titanium isopropylate, or the muriate of titanium, and wherein the volume ratio of titanium compound and alcohol is titanium compound: alcohol=1:5～20.
A kind of or its combination in the A position of lithium titanate doping lanthanum (La) element in B position doping scandium (Sc), dysprosium (Dy), holmium (Ho), erbium (Er), ytterbium (Yb), gadolinium (Gd), praseodymium (Pr), neodymium (Nd), niobium (Nb), its type of compounds is a kind of or its combination in oxide compound, nitrate, muriate, oxalate, carbonate, oxyhydroxide.
Described two-pack sequestrant is trolamine, acetic acid, lauric acid, tartrate, citric acid, oxalic acid, gluconic acid, 2,2'-dipyridyl, 1, any two kinds of combinations in 10-phenanthrolene, nitrilotriacetic acid, diethylene triaminepentaacetic acid(DTPA), quadrol, ethylenediamine tetraacetic acid (EDTA), wherein the mol ratio of sequestrant and metal ion is sequestrant: metal ion=1.0～3.0:1.
Sintering temperature described in step e is to heat up the program phase, and temperature rise rate is 2～10 ℃/min, and heated perimeter is 500～900 ℃.
Carbon source described in step h is a kind of or its combination in sucrose, chitosan, glucose, lauric acid, citric acid, and wherein the mass ratio of the carbon in sugar and lithium titanate is 1～20:100.
The present invention adopts two-pack sequestrant, alkaline synthesis condition, A, rare earth ion that it is suitable to adulterate in B position simultaneously, significantly improving reactant mixing uniformity, when improving the particle agglomeration phenomenon of material, can also obviously improve the textural defect of the octahedra 16d position of lithium titanate and tetrahedron 8a position, thereby improve the bulk conductivity rate of pure lithium titanate.Also promote in addition the table phase specific conductivity of electrode materials by coated with carbon, greatly the chemical property of the lifting electrode materials of degree.The combination electrode material Li adulterating in product rare earth ion A of the present invention, B position simultaneously
4ti
5o
12/ C is applied to the negative pole of lithium ion battery, has superior fast charging and discharging performance and good cyclical stability, can be widely used in handheld device and power cell field.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the embodiment of the present invention 1 product;
Fig. 2 is the embodiment of the present invention 2 products figure of the TEM after inert atmosphere roasting 10 h at 800 ℃;
Fig. 3 is the discharge cycles curves of the embodiment of the present invention 3 products under different multiplying;
Fig. 4 is the cyclical stabilities of the embodiment of the present invention 4 products under different multiplying;
Fig. 5 is sweep cyclic voltammetry curves speed under of the embodiment of the present invention 4 products at 0.5 mV/s.
Embodiment
The present invention is described in detail below by specific examples, but protection scope of the present invention is not limited to these embodiment.
Embodiment 1:
First according to volume ratio 1:0.1,300 mL ethanol and 30 mL water premixs are formed to mixing solutions, then add the HNO of 15 mL
3as the inhibitor of subsequent reactions; By the compound of Li and Ti, mol ratio according to Li:Ti=4.2:5 is prepared burden, take the tetra-n-butyl titanate (analytical pure) of 25.52 g, the Quilonum Retard (analytical pure) of 2.33 g, join in previous alcohol water acid mixed solution, stir by magnetic force heating stirrer, until all dissolve; Add again 0.3292 g lanthanum nitrate and 0.257 g zirconium nitrate, stir, dissolve; Again 20 g ethylenediamine tetraacetic acid (EDTA)s and 30 g citric acids are joined in mixed in advance metal ion solution, mix rear dropping 100 mL ammoniacal liquor and regulate pH value to 8, continue to stir; Be stirred into after colloidal sol until above-mentioned mixed solution, then 80 ℃ of heated and stirred are to gel state, then in the convection oven of 240 ℃, dry, and obtain the lithium titanate precursor that black is fluffy; Lithium titanate precursor is put into high energy ball mill ball milling 1 ~ 10 h, and wherein the mass ratio of ball and material is 2:1, obtains the lithium titanate precursor that particle is tiny; Then the presoma of black is put into 750 ℃ of calcining 5 h of retort furnace, obtained finished product white nanometer Li
3.95la
0.05ti
4.95zr
0.05o
12powder.Fig. 1 is the XRD figure of gained sample.Visible, the position of the each diffraction peak of XRD figure of synthetic product and relative intensity are all and Li
4ti
5o
12standard card match, wherein 32.6
othere is Li in left and right
0.35la
0.55tiO
3phase, hence one can see that, and La element is the A position that is doped to lithium titanate substantially.
Embodiment 2:
According to volume ratio 1:0.1,300 mL ethanol and 30 mL water premixs are formed to mixing solutions, then add the HCl of 15 mL as the inhibitor of subsequent reactions; By the compound of Li and Ti, mol ratio according to Li:Ti=4.2:5 is prepared burden, take the titanium isopropylate (analytical pure) of 21.31 g, the Lithium Acetate (analytical pure) of 6.43 g, join in previous alcohol water acid mixed solution, stir by magnetic force heating stirrer, until all dissolve; Add again 0.3292 g lanthanum nitrate and 0.3321 g neodymium nitrate, stir, dissolve; Again 20 g ethylenediamine tetraacetic acid (EDTA)s and 40 g citric acids are joined in mixed in advance metal ion solution, mix rear dropping 100 mL ammoniacal liquor and regulate pH value to 9, continue to stir; Be stirred into after colloidal sol until above-mentioned mixed solution, then 80 ℃ of heated and stirred are to gel state, then in the convection oven of 240 ℃, dry, and obtain the lithium titanate precursor that black is fluffy; Lithium titanate precursor is put into high energy ball mill ball milling 1 ~ 10 h, and wherein the mass ratio of ball and material is 2:1, obtains the lithium titanate precursor that particle is tiny; Then the presoma of black is put into 750 ℃ of calcining 5 h of retort furnace, obtained finished product white nano barium titanate powder for lithium; Get again 0.3 g nano lithium titanate and directly in 100 mL water, mix with 0.5589 g sucrose, add 5 mL OP9 emulsifying agents simultaneously, increase the dispersiveness of lithium titanate, after stirring 1 hour, start 80 ℃ of heating; Finally solid remaining after heating is taken out and ground, finally put into tubular type kiln roasting, pass into high-purity argon gas, maturing temperature is 800 ℃, and the time is 10 hours; Finally obtain A, the B position lithium-ion secondary cell combination electrode material Li of doped with rare-earth elements simultaneously
3.95la
0.05ti
4.95nd
0.05o
12/ C.Fig. 2 is the TEM figure of lithium titanate product, in figure, can find out Li
4ti
5o
12there is boundary clearly with the carbon-coating of 2 nm.
Embodiment 3:
According to volume ratio 1:0.2,300 mL ethanol and 60 mL water premixs are formed to mixing solutions, then add the HNO of 30 mL
3as the inhibitor of subsequent reactions; By the compound of Li and Ti, mol ratio according to Li:Ti=4.4:5 is prepared burden, take the tetra-n-butyl titanate (analytical pure) of 25.52 g, the lithium nitrate (analytical pure) of 4.55 g, join in previous alcohol water acid mixed solution, stir by magnetic force heating stirrer, until all dissolve; Add again 0.3292 g lanthanum nitrate and 0.3419 g Gadolinium trinitrate, stir, dissolve; Again 20 g ethylenediamine tetraacetic acid (EDTA)s and 60 g citric acids are joined in mixed in advance metal ion solution, mix rear dropping 110 mL ammoniacal liquor and regulate pH value to 7, continue to stir; Be stirred into after colloidal sol until above-mentioned mixed solution, then 80 ℃ of heated and stirred are to gel state, then in the convection oven of 240 ℃, dry, and obtain the lithium titanate precursor that black is fluffy; Lithium titanate precursor is put into high energy ball mill ball milling 1 ~ 10 h, and wherein the mass ratio of ball and material is 2:1, obtains the lithium titanate precursor that particle is tiny; Then the presoma of black is put into 750 ℃ of calcining 5 h of retort furnace, obtained finished product white nano barium titanate powder for lithium; Get again 0.3 g nano lithium titanate and directly in 100 mL water, mix with 0.5589 g sucrose, add 0.5 g hexadecyl benzene sulfonic acid sodium salt simultaneously, increase the dispersiveness of lithium titanate, after stirring 1 hour, start 80 ℃ of heating; Finally solid remaining after heating is taken out and ground, finally put into tubular type kiln roasting, pass into high-purity argon gas, maturing temperature is 800 ℃, and the time is 10 hours; Finally obtain A, the B position lithium-ion secondary cell combination electrode material Li of doped with rare-earth elements simultaneously
3.95la
0.05ti
4.95gd
0.05o
12/ C.Fig. 3 is for to do positive pole with this material, metal lithium sheet is made the button-shaped half-cell that negative pole is assembled into, charging and discharging curve under 1～40C different multiplying, as seen from the figure, the material of synthesized has excellent charge and discharge platform and higher reversible capacity, when 1C, loading capacity can reach 178 mAh/g, and charge and discharge platform is very smooth, demonstrates good embedding lithium performance.
Embodiment 4:
According to volume ratio 1:0.3,300 mL ethanol and 90 mL water premixs are formed to mixing solutions, then add the HCl of 30 mL as the inhibitor of subsequent reactions; By the compound of Li and Ti, mol ratio according to Li:Ti=4.4:5 is prepared burden, take the titanium isopropylate (analytical pure) of 21.31 g, the Lithium Acetate (analytical pure) of 6.74 g, join in previous alcohol water acid mixed solution, stir by magnetic force heating stirrer, until all dissolve; Add again 0.3292 g lanthanum nitrate and 0.1886 g Scium trinitrate, stir, dissolve; Again 30 g ethylenediamine tetraacetic acid (EDTA)s and 50 g citric acids are joined in mixed in advance metal ion solution, mix rear dropping 110 mL ammoniacal liquor and regulate pH value to 8, continue to stir; Be stirred into after colloidal sol until above-mentioned mixed solution, then 80 ℃ of heated and stirred are to gel state, then in the convection oven of 240 ℃, dry, and obtain the lithium titanate precursor that black is fluffy; Lithium titanate precursor is put into high energy ball mill ball milling 1 ~ 10 h, and wherein the mass ratio of ball and material is 2:1, obtains the lithium titanate precursor that particle is tiny; Then the presoma of black is put into 800 ℃ of calcining 5 h of retort furnace, obtained finished product white nano barium titanate powder for lithium; Get again 0.3 g nano lithium titanate and directly in 100 mL water, mix with 0.5589 g sucrose, add 0.5 g hexadecyl benzene sulfonic acid sodium salt simultaneously, increase the dispersiveness of lithium titanate, after stirring 1 hour, start 80 ℃ of heating; Finally solid remaining after heating is taken out and ground, finally put into tubular type kiln roasting, pass into high-purity argon gas, maturing temperature is 800 ℃, and the time is 10 hours; Finally obtain A, the B position lithium-ion secondary cell combination electrode material Li of doped with rare-earth elements simultaneously
3.95la
0.05ti
4.95sc
0.05o
12/ C.Fig. 4 is the cycle performance of this material under 1 ~ 40C discharge-rate, substantially undamped.Fig. 5 is sweep cyclic voltammetry curve speed under of this material at 0.5 mV/s, and peak shape is sharp-pointed, and polarization of electrode is less, and only has a pair of redox peak.
Claims (8)
1. lithium-ion secondary cell A, a B position preparation method for dopen Nano lithium titanate simultaneously, is characterized in that, comprises the steps:
A. ethanol and water are pressed to the volume ratio premix composition mixing solutions of 1:0～0.5, then add the inhibitor of acid as follow-up titanium (Ti) soluble compounds hydrolysis reaction, or the solvating agent of lithium (Li) slightly soluble compound;
B. by the slightly soluble of lithium and titanium or soluble compound, prepare burden according to the mol ratio of Li:Ti=0.8～1.0:1, join in the mixed solution that step a makes, by magnetic force heating stirrer stirring at normal temperature, until all dissolve;
C. by rare earth metal (RE) compound for lithium titanate A, the doping of B position, according to Li(or Ti): the mol ratio of RE=1:0.01～0.1 is prepared burden, join in the mixed solution that step b makes, by magnetic force heating stirrer stirring at normal temperature, until all dissolve;
D. by two-pack sequestrant with water premix, water and sequestrant volume ratio are 0.5～2:1, mix rear dropping ammoniacal liquor until sequestrant all dissolves, and then join in the mixed solution that step c makes, and add ammoniacal liquor to regulate pH value to 7～10, continuation stirring;
E. be stirred into after colloidal sol until the mixed solution of steps d, start heating, continue to stir simultaneously, Heating temperature is 60～100
oC, be 1～3 hour heat-up time, to gel state, then in the convection oven of 150 ℃～250 ℃, dries 3～24 hours, obtains the lithium titanate precursor of black;
F. lithium titanate precursor step e being made is put into high energy ball mill ball milling 1～10 hour, then puts into retort furnace and calcines 5～15 hours, obtains the nano barium titanate powder for lithium that rare earth element A, B position adulterate simultaneously; Wherein the rotating speed of ball milling is 300～550 r/min, and ball milling post-drying temperature is 60～200 ℃;
G. the nano lithium titanate of step f gained is directly mixed with carbon source in water, add OP series, or hexadecyl benzene sulfonic acid sodium salt is as emulsifying agent, the volume ratio of emulsifying agent and water is 0.01～0.2:1 simultaneously, after stirring 1～10 hour, start heating, temperature range is 60～100 ℃;
H. solid remaining after step g heating is taken out and ground, finally put into tubular type kiln roasting, pass into rare gas element, gas is chosen as the one in argon gas, nitrogen, helium, maturing temperature is 700 ℃～900 ℃, time is 5～20 hours, finally obtains A, the B position lithium-ion secondary cell combination electrode material Li of doped with rare-earth elements simultaneously
4ti
5o
12/ C.
2. lithium-ion secondary cell A, the B position preparation method of dopen Nano lithium titanate simultaneously according to claim 1, it is characterized in that, the described acid of step (a) is a kind of or its combination in nitric acid, hydrochloric acid, acetic acid, tartrate, oxalic acid, oxysuccinic acid, citric acid, xitix, phenylformic acid, Whitfield's ointment, coffic acid, and alcohol and sour volume ratio are alcohol: acid=1:0.01～0.1.
3. lithium-ion secondary cell A, the B position preparation method of dopen Nano lithium titanate simultaneously according to claim 1, it is characterized in that, described slightly soluble or the soluble lithium compounds of step (b) is the one in lithium nitrate, Quilonum Retard, lithium chloride, Lithium Acetate, Lithium Citrate de, lithium oxalate, lithium formate, lithium lactate, isopropyl lithium alkoxide, long-chain or short-chain alkyl lithium.
4. lithium-ion secondary cell A, the B position preparation method of dopen Nano lithium titanate simultaneously according to claim 1, it is characterized in that, the described soluble titanium compound of step (b) is tetra-n-butyl titanate, or titanium isopropylate, or the muriate of titanium, wherein the volume ratio of titanium compound and alcohol is titanium compound: alcohol=1:5～20.
5. lithium-ion secondary cell A, the B position preparation method of dopen Nano lithium titanate simultaneously according to claim 1, it is characterized in that, a kind of or its combination in the A position of lithium titanate doping lanthanum (La) element in B position doping scandium (Sc), dysprosium (Dy), holmium (Ho), erbium (Er), ytterbium (Yb), gadolinium (Gd), praseodymium (Pr), neodymium (Nd), niobium (Nb), its type of compounds is a kind of or its combination in oxide compound, nitrate, muriate, oxalate, carbonate, oxyhydroxide.
6. lithium-ion secondary cell A, the B position preparation method of dopen Nano lithium titanate simultaneously according to claim 1, it is characterized in that, described two-pack sequestrant is trolamine, acetic acid, lauric acid, tartrate, citric acid, oxalic acid, gluconic acid, 2,2'-dipyridyl, 1, any two kinds of combinations in 10-phenanthrolene, nitrilotriacetic acid, diethylene triaminepentaacetic acid(DTPA), quadrol, ethylenediamine tetraacetic acid (EDTA), wherein the mol ratio of sequestrant and metal ion is sequestrant: metal ion=1.0～3.0:1.
7. lithium-ion secondary cell A, the B position preparation method of dopen Nano lithium titanate simultaneously according to claim 1, it is characterized in that, sintering temperature described in step e is to heat up the program phase, and temperature rise rate is 2～10 ℃/min, and heated perimeter is 500～900 ℃.
8. lithium-ion secondary cell A, the B position preparation method of dopen Nano lithium titanate simultaneously according to claim 1, it is characterized in that, carbon source described in step h is a kind of or its combination in sucrose, chitosan, glucose, lauric acid, citric acid, and wherein the mass ratio of the carbon in sugar and lithium titanate is 1～20:100.
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| US20070281211A1 (en) * | 2006-06-05 | 2007-12-06 | T/J Technologies, Inc. | Alkali metal titanates and methods for their synthesis |
| CN101000960A (en) * | 2006-12-29 | 2007-07-18 | 深圳市贝特瑞电子材料有限公司 | Composite lithium titanate electrode material and preparation method thereof |
| CN101593830A (en) * | 2009-07-03 | 2009-12-02 | 郑州大学 | The preparation method of lithium ionic cell cathode material spinelle lithium titanate |
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| CN104022275A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Freeze-drying micro-emulsion method for preparing lithium titanate material for lithium-battery electrode |
| CN104022275B (en) * | 2014-05-28 | 2016-04-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Freeze drying micro emulsion legal system is ready for use on the lithium titanate material of lithium cell negative pole |
| CN104157868A (en) * | 2014-07-31 | 2014-11-19 | 上海交通大学 | Preparation method for Nb-doped Li4T5O12 nano material |
| CN104332604A (en) * | 2014-11-05 | 2015-02-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of negative electrode material lithium titanate of lithium battery |
| CN104332604B (en) * | 2014-11-05 | 2016-08-24 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of lithium cell negative pole material lithium titanate |
| CN107293720A (en) * | 2017-06-28 | 2017-10-24 | 合肥国轩高科动力能源有限公司 | A kind of zirconium scandium composite oxides cladding lithium titanate anode material and preparation method thereof |
| CN107293720B (en) * | 2017-06-28 | 2019-12-10 | 合肥国轩高科动力能源有限公司 | Zirconium-scandium composite oxide coated lithium titanate negative electrode material and preparation method thereof |
| CN110459750A (en) * | 2019-08-21 | 2019-11-15 | 宋婷 | A kind of cathode material of lithium-ion power battery and preparation method thereof |
| CN110571428A (en) * | 2019-09-16 | 2019-12-13 | 广东工业大学 | Pure-phase lithium titanate negative electrode material, preparation method thereof, negative electrode and battery |
| CN110563031A (en) * | 2019-09-16 | 2019-12-13 | 广东工业大学 | Lithium titanate negative electrode material, preparation method thereof and battery |
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