CN103771500B - 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 rechargeable battery nanometer combined electrode material lithium titanate, particularly relate to the preparation method of the coated combination electrode material lithium titanate of the carbon that simultaneously adulterates a kind of rare earth ion A, B position.
Background technology
The advantage such as lithium rechargeable battery 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 field such as electric bicycle, electric automobile.In current existing battery system, lithium secondary battery is acknowledged as and can meets electric motor car better to one of electrokinetic cell of power stage, operating range, acceleration capacity, useful life and specific energy density requirement.At present, the negative material of business-like lithium ion battery adopts all kinds of material with carbon element mostly, but it also exists some inevitable defects: during Battery formation, reacts form SEI film with electrolyte, causes the consumption of electrolyte and lower coulombic efficiency first; During over-charging of battery, at carbon electrodes precipitating metal lithium, Li dendrite may be formed and causes short circuit, cause temperature to raise, battery explosion; In addition, the diffusion coefficient of lithium ion in material with carbon element is less, causes battery not realize high current charge-discharge, thus limits the range of application of lithium ion battery.
Spinel-type Li
4ti
5o
12as a kind of novel negative material, owing to having higher electrode potential (~ 1.55V, relative to metal Li), Li dendrite is inhibit to separate out on negative pole, solve the internal short-circuit problem of battery, thus improve the fail safe of battery, become current study hotspot.In addition, Li
4ti
5o
12be a kind of " zero strain " material, cell parameter changes hardly at Lithium-ion embeding with before and after deviating from, thus makes it have excellent cycle performance and stable discharge voltage.At normal temperatures, lithium ion exceeds an order of magnitude at the diffusion 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
12conductivity very low, be close to insulation, the poor-performing under high magnification, if be applied to the field such as power car, large-scale energy-storage battery will be subject to great restriction.Thus, for Li
4ti
5o
12the shortcoming of material conductivity difference, the research improving its conductivity and high rate capability seems particularly important.At present, usually said ion doping is at A position (Li position), B position (Ti position) or O position Doped ions, improves the defect sturcture of lithium titanate, improves the conductivity of material itself, reduces the resistance of electrode material, tentatively promotes electrode performance with this.
Rare earth metal doping effectively can improve the 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 is mostly directly doped to B position, particle agglomeration is relatively more serious, can affect the performance of battery to a certain extent or can not play effect that thulium improves conductivity to greatest extent.
Summary of the invention
The object of the invention is to overcome prior art and prepare the defect that the high magnification existed in lithium titanate anode material transfers poor electrical performance, provide a kind of and prepare the method with the composite material lithium titanate of excellent electrochemical performance by simultaneously rare-earth metal doped in A, B position and in conjunction with bi-component chelating agent sol-gal process.The coated combination electrode material lithium titanate of the carbon that simultaneously adulterates of standby A, B position of this legal system no matter shows mutually or the conductivity of body phase is obtained for lifting, demonstrates excellent high rate performance and cycle performance.
For reaching above-mentioned expection object, the present invention adopts following technical scheme:
The while of lithium rechargeable battery A, B position, a preparation method for dopen Nano lithium titanate, is characterized in that, comprise the steps:
A. volume ratio premix ethanol and water being pressed 1:0 ~ 0.5 forms mixed solution, then adds the inhibitor of acid as follow-up titanium (Ti) soluble compounds hydrolysis, or the lytic 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 obtained mixed liquor of step a, by magnetic force heating stirrer stirring at normal temperature, until all dissolve;
C. rare earth metal (RE) compound of lithium titanate A, B position doping will be used for, according to Li(or Ti): the mol ratio of RE=1:0.01 ~ 0.1 is prepared burden, join in the obtained mixed liquor of step b, by magnetic force heating stirrer stirring at normal temperature, until all dissolve;
D. bi-component chelating agent is followed water premix, water and chelating agent volume ratio are 0.5 ~ 2:1, mix rear dropping ammoniacal liquor until chelating agent all dissolves, and then join in the obtained mixed liquor of step c, and add ammoniacal liquor adjust ph to 7 ~ 10, continue to stir;
E. after the mixed liquor of steps d is stirred into colloidal sol, start heating, continue to stir, heating-up temperature is 60 ~ 100 simultaneously
oC, heating time is 1 ~ 3 hour, to gel state, then dries 3 ~ 24 hours in the convection oven of 150 DEG C ~ 250 DEG C, obtains the lithium titanate precursor of black;
F. the lithium titanate precursor that step e is obtained is put into high energy ball mill ball milling 1 ~ 10 hour, then put into Muffle furnace calcining 5 ~ 15 hours, obtain the nano barium titanate powder for lithium adulterated in rare earth element A, B position simultaneously; Wherein the rotating speed of ball milling is 300 ~ 550 r/min, and ball milling post-baking temperature is 60 ~ 200 DEG C;
G. the nano lithium titanate of step f gained is directly mixed with carbon source in water, add OP series, or cetyl benzenesulfonic acid sodium is as emulsifying agent, the volume ratio of emulsifying agent and water is 0.01 ~ 0.2:1 simultaneously, start heating after 1 ~ 10 hour to be mixed, temperature range is 60 ~ 100 DEG C;
H. solid remaining after step g heating is taken out grinding, finally put into tubular type kiln roasting, pass into inert gas, gas is chosen as the one in argon gas, nitrogen, helium, sintering temperature is 700 DEG C ~ 900 DEG C, time is 5 ~ 20 hours, finally obtains the lithium rechargeable battery combination electrode material Li of doped with rare-earth elements while of A, B position
4ti
5o
12/ C.
Acid described in step (a) is one in nitric acid, hydrochloric acid, acetic acid, tartaric acid, oxalic acid, malic acid, citric acid, ascorbic acid, benzoic acid, salicylic acid, caffeic acid or its combination, and alcohol is alcohol with the volume ratio of acid: acid=1:0.01 ~ 0.1.
Slightly soluble described in step (b) or soluble lithium compounds are the one in lithium nitrate, lithium carbonate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, lithium formate, lithium lactate, isopropyl lithium alkoxide, long-chain or short-chain alkyl lithium.
Soluble titanium compound described in step (b) is tetra-n-butyl titanate, or tetraisopropyl titanate, or the chloride of titanium, and wherein the volume ratio of titanium compound and alcohol is titanium compound: alcohol=1:5 ~ 20.
While 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), one in niobium (Nb) or its combination, its type of compounds is one in oxide, nitrate, chloride, oxalates, carbonate, hydroxide or its combination.
Described bi-component chelating agent is triethanolamine, acetic acid, laurate, tartaric acid, citric acid, oxalic acid, gluconic acid, 2,2'-bipyridine, 1, any two kinds of combinations in 10-phenanthrolene, aminotriacetic acid, diethylene-triamine pentaacetic acid, ethylenediamine, ethylenediamine tetra-acetic acid, wherein the mol ratio of chelating agent and metal ion is chelating agent: metal ion=1.0 ~ 3.0:1.
Sintering temperature described in step e is heat up the program phase, and heating rate is 2 ~ 10 DEG C/min, and heated perimeter is 500 ~ 900 DEG C.
Carbon source described in step h is one in sucrose, shitosan, glucose, laurate, citric acid or its combination, and the carbon wherein in sugar and the mass ratio of lithium titanate are 1 ~ 20:100.
The present invention adopts bi-component chelating agent, alkaline synthesis condition, suitable rare earth ion is adulterated in A, B position simultaneously, significantly improving reactant mixing uniformity, obviously can also improve the fault of construction of the octahedra 16d position of lithium titanate and tetrahedron 8a position while improving the particle agglomeration phenomenon of material, thus improve the bulk conductivity rate of pure lithium titanate.Also promoted the table phase conductivity of electrode material in addition by coated with carbon, the chemical property of the lifting electrode material of high degree.The combination electrode material Li adulterated in product rare earth ion A, B position of the present invention 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 portable set and electrokinetic cell field.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the embodiment of the present invention 1 product;
Fig. 2 is the TEM figure of the embodiment of the present invention 2 product at 800 DEG C after inert atmosphere roasting 10 h;
Fig. 3 is the discharge cycles curve of the embodiment of the present invention 3 product under different multiplying;
Fig. 4 is the cyclical stability of the embodiment of the present invention 4 product under different multiplying;
Fig. 5 is the embodiment of the present invention 4 product at the cyclic voltammetry curve swept under speed of 0.5 mV/s.
Embodiment
The present invention is described in detail below by instantiation, but protection scope of the present invention is not limited to these embodiments.
Embodiment 1:
First according to volume ratio 1:0.1,300 mL ethanol and 30 mL water premixs are formed mixed solution, then add the HNO of 15 mL
3as the inhibitor of subsequent reactions; By the compound of Li and Ti, prepare burden according to the mol ratio of Li:Ti=4.2:5, take the tetra-n-butyl titanate (analyzing pure) of 25.52 g, the lithium carbonate (analyzing pure) of 2.33 g, join in previous alcohol water acid mixed liquor, stirred by magnetic force heating stirrer, until all dissolve; Add 0.3292 g lanthanum nitrate and 0.257 g zirconium nitrate again, stir, dissolve; Again 20 g ethylenediamine tetra-acetic acids and 30 g citric acids are joined in metal ion solution mixed in advance, mix rear dropping 100 mL ammoniacal liquor adjust ph to 8, continue to stir; After above-mentioned mixed liquor is stirred into colloidal sol, then 80 DEG C of heating are stirred to gel state, then dry in the convection oven of 240 DEG C, obtain the lithium titanate precursor that black is fluffy; Lithium titanate precursor is put into high energy ball mill ball milling 1 ~ 10 h, 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 Muffle furnace 750 DEG C calcining 5 h, obtain 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 XRD of synthetic product schemes the position of each diffraction maximum and relative intensity is equal and Li
4ti
5o
12standard card match, wherein 32.6
othere is Li in left and right
0.35la
0.55tiO
3phase, it can thus be appreciated that La element is the A position being doped to lithium titanate substantially.
Embodiment 2:
According to volume ratio 1:0.1,300 mL ethanol and 30 mL water premixs are formed mixed solution, then add the inhibitor of HCl as subsequent reactions of 15 mL; By the compound of Li and Ti, prepare burden according to the mol ratio of Li:Ti=4.2:5, take the tetraisopropyl titanate (analyzing pure) of 21.31 g, the lithium acetate (analyzing pure) of 6.43 g, join in previous alcohol water acid mixed liquor, stirred by magnetic force heating stirrer, until all dissolve; Add 0.3292 g lanthanum nitrate and 0.3321 g neodymium nitrate again, stir, dissolve; Again 20 g ethylenediamine tetra-acetic acids and 40 g citric acids are joined in metal ion solution mixed in advance, mix rear dropping 100 mL ammoniacal liquor adjust ph to 9, continue to stir; After above-mentioned mixed liquor is stirred into colloidal sol, then 80 DEG C of heating are stirred to gel state, then dry in the convection oven of 240 DEG C, obtain the lithium titanate precursor that black is fluffy; Lithium titanate precursor is put into high energy ball mill ball milling 1 ~ 10 h, 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 Muffle furnace 750 DEG C calcining 5 h, obtain finished product white nano barium titanate powder for lithium; Get 0.3 g nano lithium titanate more directly to mix in 100 mL water with 0.5589 g sucrose, add 5 mL OP9 emulsifying agents simultaneously, increase the dispersiveness of lithium titanate, after 1 hour to be mixed, start 80 DEG C of heating; Finally the solid be left after heating is taken out grinding, finally put into tubular type kiln roasting, pass into high-purity argon gas, sintering temperature is 800 DEG C, and the time is 10 hours; Finally obtain the lithium rechargeable battery combination electrode material Li of doped with rare-earth elements while of A, B position
3.95la
0.05ti
4.95nd
0.05o
12/ C.Fig. 2 is the TEM figure of lithium titanate product, can find out Li in figure
4ti
5o
12boundary is clearly had 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 mixed solution, then add the HNO of 30 mL
3as the inhibitor of subsequent reactions; By the compound of Li and Ti, prepare burden according to the mol ratio of Li:Ti=4.4:5, take the tetra-n-butyl titanate (analyzing pure) of 25.52 g, the lithium nitrate (analyzing pure) of 4.55 g, join in previous alcohol water acid mixed liquor, stirred by magnetic force heating stirrer, until all dissolve; Add 0.3292 g lanthanum nitrate and 0.3419 g gadolinium nitrate again, stir, dissolve; Again 20 g ethylenediamine tetra-acetic acids and 60 g citric acids are joined in metal ion solution mixed in advance, mix rear dropping 110 mL ammoniacal liquor adjust ph to 7, continue to stir; After above-mentioned mixed liquor is stirred into colloidal sol, then 80 DEG C of heating are stirred to gel state, then dry in the convection oven of 240 DEG C, obtain the lithium titanate precursor that black is fluffy; Lithium titanate precursor is put into high energy ball mill ball milling 1 ~ 10 h, 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 Muffle furnace 750 DEG C calcining 5 h, obtain finished product white nano barium titanate powder for lithium; Get 0.3 g nano lithium titanate more directly to mix in 100 mL water with 0.5589 g sucrose, add 0.5 g cetyl benzenesulfonic acid sodium simultaneously, increase the dispersiveness of lithium titanate, after 1 hour to be mixed, start 80 DEG C of heating; Finally the solid be left after heating is taken out grinding, finally put into tubular type kiln roasting, pass into high-purity argon gas, sintering temperature is 800 DEG C, and the time is 10 hours; Finally obtain the lithium rechargeable battery combination electrode material Li of doped with rare-earth elements while of A, B position
3.95la
0.05ti
4.95gd
0.05o
12/ C.Fig. 3 is for do positive pole with this material, metal lithium sheet makees 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, synthesized material has excellent charge and discharge platform and higher reversible capacity, during 1C, discharge 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 mixed solution, then add the inhibitor of HCl as subsequent reactions of 30 mL; By the compound of Li and Ti, prepare burden according to the mol ratio of Li:Ti=4.4:5, take the tetraisopropyl titanate (analyzing pure) of 21.31 g, the lithium acetate (analyzing pure) of 6.74 g, join in previous alcohol water acid mixed liquor, stirred by magnetic force heating stirrer, until all dissolve; Add 0.3292 g lanthanum nitrate and 0.1886 g scandium nitrate again, stir, dissolve; Again 30 g ethylenediamine tetra-acetic acids and 50 g citric acids are joined in metal ion solution mixed in advance, mix rear dropping 110 mL ammoniacal liquor adjust ph to 8, continue to stir; After above-mentioned mixed liquor is stirred into colloidal sol, then 80 DEG C of heating are stirred to gel state, then dry in the convection oven of 240 DEG C, obtain the lithium titanate precursor that black is fluffy; Lithium titanate precursor is put into high energy ball mill ball milling 1 ~ 10 h, 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 Muffle furnace 800 DEG C calcining 5 h, obtain finished product white nano barium titanate powder for lithium; Get 0.3 g nano lithium titanate more directly to mix in 100 mL water with 0.5589 g sucrose, add 0.5 g cetyl benzenesulfonic acid sodium simultaneously, increase the dispersiveness of lithium titanate, after 1 hour to be mixed, start 80 DEG C of heating; Finally the solid be left after heating is taken out grinding, finally put into tubular type kiln roasting, pass into high-purity argon gas, sintering temperature is 800 DEG C, and the time is 10 hours; Finally obtain the lithium rechargeable battery combination electrode material Li of doped with rare-earth elements while of A, B position
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 this material at the cyclic voltammetry curve swept under speed of 0.5 mV/s, and peak shape is sharp-pointed, and electrode polarization is less, and only has a pair redox peak.
Claims (9)
1. a preparation method for lithium rechargeable battery A, B position simultaneously dopen Nano lithium titanate, is characterized in that, comprise the steps:
A. volume ratio premix ethanol and water being pressed 1:0 ~ 0.5 forms mixed solution, then adds the inhibitor of acid as follow-up titanium (Ti) soluble compounds hydrolysis, or the lytic 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 obtained mixed liquor of step a, by magnetic force heating stirrer stirring at normal temperature, until all dissolve;
C. by being used for rare earth metal (RE) compound of lithium titanate A, B position doping, preparing burden according to the mol ratio of Li or Ti:RE=1:0.01 ~ 0.1, joining in the obtained mixed liquor of step b, by magnetic force heating stirrer stirring at normal temperature, until all dissolve;
D. bi-component chelating agent is followed water premix, water and chelating agent volume ratio are 0.5 ~ 2:1, mix rear dropping ammoniacal liquor until chelating agent all dissolves, and then join in the obtained mixed liquor of step c, and add ammoniacal liquor adjust ph to 7 ~ 10, continue to stir;
E. after the mixed liquor of steps d is stirred into colloidal sol, start heating, continue to stir simultaneously, heating-up temperature is 60 ~ 100 DEG C, and heating time is 1 ~ 3 hour, to gel state, then dry 3 ~ 24 hours in the convection oven of 150 DEG C ~ 250 DEG C, obtain the lithium titanate precursor of black;
F. the lithium titanate precursor that step e is obtained is put into high energy ball mill ball milling 1 ~ 10 hour, then put into Muffle furnace calcining 5 ~ 15 hours, obtain the nano barium titanate powder for lithium adulterated in rare earth element A, B position simultaneously; Wherein the rotating speed of ball milling is 300 ~ 550 r/min, and ball milling post-baking temperature is 60 ~ 200 DEG C.
2. the preparation method of lithium rechargeable battery A, B position simultaneously dopen Nano lithium titanate according to claim 1, it is characterized in that, acid described in step (a) is one in nitric acid, hydrochloric acid, acetic acid, tartaric acid, oxalic acid, malic acid, citric acid, ascorbic acid, benzoic acid, salicylic acid, caffeic acid or its combination, and alcohol is alcohol with the volume ratio of acid: acid=1:0.01 ~ 0.1.
3. the preparation method of lithium rechargeable battery A, B position simultaneously dopen Nano lithium titanate according to claim 1, it is characterized in that, the slightly soluble described in step (b) or soluble lithium compounds are the one in lithium nitrate, lithium carbonate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, lithium formate, lithium lactate, isopropyl lithium alkoxide, long-chain or short-chain alkyl lithium.
4. the preparation method of lithium rechargeable battery A, B position simultaneously dopen Nano lithium titanate according to claim 1, it is characterized in that, soluble titanium compound described in step (b) is tetra-n-butyl titanate, or tetraisopropyl titanate, or the chloride of titanium, wherein the volume ratio of titanium compound and alcohol is titanium compound: alcohol=1:5 ~ 20.
5. the preparation method of lithium rechargeable battery A, B position simultaneously dopen Nano lithium titanate according to claim 1, it is characterized in that, while 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), one in neodymium (Nd) or its combination, its type of compounds is one in oxide, nitrate, chloride, oxalates, carbonate, hydroxide or its combination.
6. the preparation method of lithium rechargeable battery A, B position simultaneously dopen Nano lithium titanate according to claim 1, it is characterized in that, described bi-component chelating agent is triethanolamine, acetic acid, laurate, tartaric acid, citric acid, oxalic acid, gluconic acid, 2,2'-bipyridine, 1, any two kinds of combinations in 10-phenanthrolene, aminotriacetic acid, diethylene-triamine pentaacetic acid, ethylenediamine, ethylenediamine tetra-acetic acid, wherein the mol ratio of chelating agent and metal ion is chelating agent: metal ion=1.0 ~ 3.0:1.
7. the preparation method of lithium rechargeable battery A, B position simultaneously dopen Nano lithium titanate according to claim 1, it is characterized in that, sintering temperature described in step f is heat up the program phase, and heating rate is 2 ~ 10 DEG C/min, and heated perimeter is 500 ~ 900 DEG C.
8. the lithium rechargeable battery combination electrode material Li of A, B position doped with rare-earth elements simultaneously
4ti
5o
12the preparation method of/C, is characterized in that, comprises the steps:
The nano lithium titanate of A, B position g. method according to claim 1 prepared doped with rare-earth elements simultaneously directly mixes with carbon source in water, add OP series simultaneously, or cetyl benzenesulfonic acid sodium is as emulsifying agent, the volume ratio of emulsifying agent and water is 0.01 ~ 0.2:1, start heating after 1 ~ 10 hour to be mixed, temperature range is 60 ~ 100 DEG C;
H. solid remaining after step g heating is taken out grinding, finally put into tubular type kiln roasting, pass into inert gas, gas is chosen as the one in argon gas, nitrogen, helium, sintering temperature is 700 DEG C ~ 900 DEG C, time is 5 ~ 20 hours, finally obtains the lithium rechargeable battery combination electrode material Li of doped with rare-earth elements while of A, B position
4ti
5o
12/ C.
9. the lithium rechargeable battery combination electrode material Li of a kind of A, B position doped with rare-earth elements simultaneously according to claim 8
4ti
5o
12the preparation method of/C, is characterized in that, the carbon source described in step g is one in sucrose, shitosan, glucose, laurate, citric acid or its combination, and the carbon wherein in sugar and the mass ratio of lithium titanate are 1 ~ 20:100.
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| CN104157868B (en) * | 2014-07-31 | 2016-06-01 | 上海交通大学 | The Li that a kind of Nb adulterates4Ti5O12The preparation method of nano material |
| 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 |
| 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 |
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| 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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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| CN109216634A (en) * | 2017-07-07 | 2019-01-15 | 通用汽车环球科技运作有限责任公司 | For inhibiting or minimizing the transition metal ions in lithium ion battery and the polymer ions trap of dendritic crystal formation or growth |
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