CN102760876B - Niobate and niobate composite material and application of niobate composite material to secondary lithium battery - Google Patents

Niobate and niobate composite material and application of niobate composite material to secondary lithium battery Download PDF

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CN102760876B
CN102760876B CN201110112041.6A CN201110112041A CN102760876B CN 102760876 B CN102760876 B CN 102760876B CN 201110112041 A CN201110112041 A CN 201110112041A CN 102760876 B CN102760876 B CN 102760876B
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niobates
composite material
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niobate
carbon
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CN102760876A (en
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简泽浪
卢侠
方铮
胡勇胜
陈立泉
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Institute of Physics of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides niobate and a niobate composite material and application of the niobate to a secondary lithium battery. The niobate has a general formula of LaMbNbcOd, wherein L is selected from one or more of Li, Na or K; M is selected from one or more of B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La and Ta; and a, b, c and d stand for molar percentage, wherein a is not less than 0.8 and not more than 1.1, b is not less than 0 and less than 0.2, c is not less than 2.9 and not more than 3.1, and d is not less than 7.8 and not more than 8. The niobate and the niobate composite material which are used as a cathode of the secondary lithium ion battery are high in capacity, can be well circulated, are superior to the lithium titanate material in the market and is a potential material for replacing the lithium titanate.

Description

Niobates and composite material thereof and its application in serondary lithium battery
Technical field
The present invention relates to niobates and composite material and its thereof application in serondary lithium battery, in particular to niobates and composite material thereof, its preparation method and containing the negative pole of this material and composite material and battery.
Background technology
(Acta Chemica Scandinavica., 25, (1971) 3337 in early days; Journal of CrystalGrowth.18, (1973) 179-184; Journal of the European Ceramic Society., 26, (2006) 2031-2034) to LiNb 3o 8research concentrate on the preparation of its material, structure and its application in ceramic.S.O.Yoon, J.H.Yoon, et al is by high-purity Li 2cO 3powder and Nb 2o 5fire 700-850 DEG C after powder mixing and obtain LiNb 3o 8, then with TiO 2burn till fine and close pottery at 1200-1350 DEG C, can use as ceramic material.
M.Anji Reddy, has delivered " Facile insertion oflithium into nanocrystalline AlNbO for 2008 on Chem.Mater. magazine 4at room temperature " article, give nano-aluminum nitride bO 4there is good electro-chemical activity.Within 2011, Goodenough professor has delivered " New Anode Framework for Rechargeable Lithium Batteries " at Chemistry ofMaterials, the TiNb that carbon is coated 2o 7in the discharge and recharge interval of 2.5 ~ 1.0V, show good performance.The application of niobium base oxide in battery, obtains extensive research.Business-like a kind of lithium battery cathode material lithium titanate (Li on this and market 4ti 5o 12) compare and have larger energy storage advantage, the theoretical capacity of lithium titanate is greatly about 175mAh/g, although lithium titanate has good cycle performance, itself electronic conductance is not high, need relevant modification could improve its conductance, and its theoretical capacity is on the low side.
Nb in niobates 5+/ Nb 4+and Nb 4+/ Nb 3+ oxidation-reduction pair between 1 ~ 3V, 2 electro transfer can be realized, therefore there is very high theoretical capacity.But as the material of broad stopband, the electronic conductance of niobates is also bad, in actual applications, require that niobates electrode material has higher electronic conductance and ionic conductance simultaneously, the stability of structure, and good conductivity between holding electrode material, also will have stable crystal boundary and less volume deformation, and ion transport is unobstructed.
Summary of the invention
In order to overcome above-mentioned defect, an object of the present invention is to provide a kind of niobates in the application preparing electrode material in serondary lithium battery, the application preferably in negative material.
Above-mentioned niobates has following general formula: L am bnb co d,
L is selected from one or more of Li, Na or K;
M is selected from one or more in B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, Ta;
A, b, c, d represent molar percentage, 0.8≤a≤1.1,0≤b < 0.2,2.9≤c≤3.1,7.8≤d≤8.
7.8≤d≤8 can indicate the situation that Lacking oxygen exists, and the cation of available low price substitutes Nb.
Wherein, in a specific embodiments, niobates is prepared by solid phase method and obtains, and the method comprises the steps:
By L source, M source and Nb 2o 5powder is according to L am bnb co dafter molar ratio ingredient, add solvent dilution and become white paste; Above-mentioned pastel is dry under a little more than the environment of room temperature after ball milling, compressing tablet after cooling.By above-mentioned white plates as Al 2o 3in crucible, then Fast Heating in atmosphere, temperature between 700-1000 DEG C, and obtains L after being incubated a few hours am bnb co d.
Further above-mentioned L am bnb co dbe placed in argon gas or nitrogen, 700-800 DEG C of heating 5-24h, obtains the niobates containing Lacking oxygen.
Wherein, in further specific embodiments, niobates prepares by the following method:
By Nb (OH) 5aqueous citric acid solution is dissolved in, according to L at 80 DEG C am bnb co din the proportioning of each element, after L source and M source are added batching, continuous heating, forms colloidal sol, by colloidal sol as in baking oven, finally forms gel, gel is transferred to Al 2o 3in crucible, then heat in atmosphere, temperature between 500-700 DEG C, and is incubated a few hours, obtains nano level L after cooling am bnb co d.
Preferably, L source is containing the material containing Li, Na or K oxide after Li, Na or K or decomposes.
Preferably, M source is containing the material containing B, Al, Ti, V, Cr, Mn, Fe, Co or Ni oxide after B, Al, Ti, V, Cr, Mn, Fe, Co or Ni or decomposes.
Of the present invention have an object to be to provide a kind of niobates composite material.
Above-mentioned niobates composite material has following general formula: C-L am bnb co d,
C is carbon, and described carbon is coated on the surface of niobates particle;
L is selected from one or more of Li, Na or K;
M is selected from one or more in B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, Ta;
A, b, c, d represent molar percentage, 0.8≤a≤1.1,0≤b < 0.2,2.9≤c≤3.1,7.8≤d≤8.
7.8≤d≤8 can indicate the situation that Lacking oxygen exists, and concrete operations can substitute Nb with cation (Ti, Mn etc.) at a low price.
The mass percentage of described carbon is less than or equal to 20% for being greater than zero, is preferably 0.1%-10%.
Wherein, in a specific embodiments, niobates is prepared by solid phase method and obtains, and the method comprises the steps:
By L source, M source and Nb 2o 5powder is according to L am bnb co dafter molar ratio ingredient, add solvent dilution and become white paste; Above-mentioned pastel is dry under a little more than the environment of room temperature after ball milling, compressing tablet after cooling.By above-mentioned white plates as Al 2o 3in crucible, then Fast Heating in atmosphere, temperature between 700-1000 DEG C, and obtains L after being incubated a few hours am bnb co d.
Further above-mentioned L am bnb co dbe placed in argon gas or nitrogen, 700-800 DEG C of heating 5-24h, obtains the niobates containing Lacking oxygen.
Wherein, in further specific embodiments, niobates prepares by the following method:
By Nb (OH) 5aqueous citric acid solution is dissolved in, according to L at 80 DEG C am bnb co din the proportioning of each element, after L source and M source are added batching, continuous heating, forms colloidal sol, by colloidal sol as in baking oven, finally forms gel, gel is transferred to Al 2o 3in crucible, then heat in atmosphere, temperature between 500-700 DEG C, and is incubated a few hours, obtains nano level L after cooling am bnb co d.
Preferably, L source is containing the material containing Li, Na or K oxide after Li, Na or K or decomposes.
Preferably, M source is containing the material containing B, Al, Ti, V, Cr, Mn, Fe, Co or Ni oxide after B, Al, Ti, V, Cr, Mn, Fe, Co or Ni or decomposes.
Wherein, the method for carrying out the coated process of carbon comprises the steps:
By described niobates with containing after carbon compound Homogeneous phase mixing in an inert atmosphere 400 ~ 800 DEG C heat a few hours, after fully reacting, after cooling, obtain niobates composite material.
Wherein, described containing carbon compound to be heating-up temperature interval the be organic compound of 400 ~ 700 DEG C.Preferably sucrose, glucose or ionic liquid, ionic liquid is [EMIm] [N (CN) preferably 2].
Another object of the present invention is to provide a kind of niobates composite material and is preparing the application of electrode material of serondary lithium battery.
The electrode material of above-mentioned serondary lithium battery, as negative material.
Another object of the present invention is to provide a kind of negative pole of serondary lithium battery.
Particularly, this negative pole comprises collector and the negative material of load on this collector, and described negative material is above-mentioned niobates and composite material thereof.
Wherein, the common negative current collector that collector can adopt this field of batteries known, there is no particular limitation.
Further object of the present invention is to provide a kind of lithium battery, this battery positive pole, negative pole and electrolyte, and described negative pole is the above-mentioned negative pole containing niobates of the present invention and composite material thereof.
Adopt niobates of the present invention and niobates composite material to be applicable to various energy storage device as the above-mentioned serondary lithium battery of negative pole, such as, can be applied to portable energy-storing equipment, electric automobile and electric tool, back-up source, redundant electrical power, be not limited to this.
Compared with prior art, the present invention at least possesses following beneficial effect:
1, the present invention has prepared a kind of novel secondary lithium battery negative material.
2, niobates of the present invention and composite material thereof are as its first all discharge and recharge 0-3V voltage inner capacities of negative pole of secondary lithium battery up to 283mAh/g, and can be good at circulation; After ball milling, with material with carbon element Homogeneous phase mixing, in 1-3V voltage range, reversible capacity can reach more than 210mAh/g, and capacity can be stabilized in more than 180mAh/g, is better than the upper lithium titanate material in market, capacity is 160mAh/g, is one of potential material replacing lithium titanate.
3, can as the negative material of lithium ion battery containing niobates of the present invention and composite material thereof, have good cycle performance, fail safe is high, pollution-free, low price, technique is simple, be widely used, be expected to the lithium titanate (Li replacing extensively research now 4ti 5o 12) material, portable energy-storing equipment, electric automobile and electric tool, back-up source, redundant electrical power etc. can be applied to.
4, preparation technology of the present invention is simple, meets modernization large-scale production completely, has huge application prospect.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 is the X-ray diffractogram of niobates of the present invention;
Fig. 2 be niobates of the present invention in 0-3V voltage range, current density is the charging and discharging curve of 20mAh/g;
Fig. 3 be the niobates that obtains after high-energy ball milling of the present invention in 1-3V voltage range, current density is the charging and discharging curve of 20mA/g.
The niobates that the present invention that Fig. 4 is obtains after high-energy ball milling is in 1-3V voltage range, and current density is the charge and discharge cycles process of 20mA/g.
Fig. 5 be the niobates composite material that obtains after carbon is coated of the present invention in 1-3V voltage range, current density is the charging and discharging curve of 20mA/g.
Fig. 6 be the niobates that obtains of sol-gal process of the present invention in 1-3V voltage range, current density is the charging and discharging curve of 20mA/g.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.But these embodiments are only limitted to illustrate that the present invention and being not used in limits the scope of the invention.
embodiment 1
According to LiNb 3o 8in the proportioning of each element get highly purified Li respectively 2cO 3powder and Nb 2o 5powder adds alcohol and is diluted to white paste; Compressing tablet after Drying and cooling, is warming up to 800 DEG C with the heating rate of 5 DEG C/min in atmosphere, and obtains pure sample after being incubated 2 hours.Fig. 1 gives pure phase LiNb 3o 8xRD diffracting spectrum.
embodiment 2
According to LiNb 3o 8in the proportioning of each element get highly purified Li respectively 2cO 3powder and Nb 2o 5powder adds alcohol and is diluted to white paste; After Drying and cooling, compressing tablet is warming up to 800 DEG C with the heating rate of 5 DEG C/min in atmosphere, and is incubated 2 hours, can obtain required niobates LiNb 3o 8.
According to LiNb 3o 8, acetylene black, PVDF respectively accounts for 80%, and the proportioning of 10%, 10% is prepared into electrode, as an electrode of half-cell, adopts lithium metal, with the LiPF of 1mol/L to electrode 6(EC-divinyl carbonic ester (DEC) (volume ratio 1: 1 of EC and DEC), as electrolyte, is assembled into battery and carries out charge-discharge test to its battery/vinyl carbonate in glove box.Voltage range is at 0-3V, and current density is 20mA/g, and test result is shown in Fig. 2.
embodiment 3
According to LiNb 3o 8in the proportioning of each element get highly purified Li respectively 2cO 3powder and Nb 2o 5powder adds alcohol and is diluted to white paste; Compressing tablet after Drying and cooling, is warming up to 800 DEG C with the heating rate of 5 DEG C/min in atmosphere, and obtains required niobates LiNb after being incubated 2 hours 3o 8.The sample obtained can be obtained after the high-energy ball milling of 24h the particle of below 100nm.Embodiment 2 is copied to do charge-discharge test.Voltage range is at 1-3V, and current density is 20mA/g, and test result is shown in Fig. 3 and Fig. 4.
embodiment 4
According to LiNb 3o 8in the proportioning of each element get highly purified Li respectively 2cO 3powder and Nb2O5 powder add alcohol and are diluted to white paste; Compressing tablet after Drying and cooling, is warming up to 800 DEG C with the heating rate of 5 DEG C/min in atmosphere, and is incubated 2 hours, can obtain required niobates LiNb 3o 8.
By the LiNb prepared 3o 8after powder and sucrose Homogeneous phase mixing in an inert atmosphere 700 DEG C heat 4h, obtain the niobates composite material that C is coated after cooling: C-LiNb 3o 8.Copy embodiment 3 to do charge-discharge test, test result is shown in Fig. 5.
embodiment 5
By Nb (OH) 5at 80 DEG C, be dissolved in citric acid, add LiNO for n (Li)/n (Nb)=1: 3 in molar ratio 3powder, after LiNO3 dissolves completely, continuous heating, forms colloidal sol, by colloidal sol as in baking oven, finally forms gel, gel is transferred to Al 2o 3in crucible, then heat in atmosphere, temperature at 600 DEG C, and obtains required nanometer niobates LiNb after being incubated 2 hours 3o 8.Copy embodiment 3 to do charge-discharge test, test result is shown in Fig. 6.
embodiment 6
According to LiNb 3o 8in the proportioning of each element get highly purified Li respectively 2cO 3powder and Nb 2o 5powder adds alcohol and is diluted to white paste; Drying and cooling sheet, is warming up to 800 DEG C with the heating rate of 5 DEG C/min in atmosphere, and is incubated 2 hours, can obtain the niobates LiNb of required pure sample 3o 8material.
By the LiNb prepared 3o 8be placed in argon gas or nitrogen, 700 DEG C of heating 5h, obtain the niobates LiNb containing Lacking oxygen 3o 7.9.Copy embodiment 3 to do charge-discharge test, analog result is in table 1.
embodiment 7
According to LiNb 3o 8in the proportioning of each element get highly purified Li respectively 2cO 3powder and Nb 2o 5powder adds alcohol and is diluted to white paste; Compressing tablet after Drying and cooling, is warming up to 800 DEG C with the heating rate of 5 DEG C/min in atmosphere, and is incubated 2 hours, can obtain the niobates LiNb of required pure sample 3o 8.
By the LiNb prepared 3o 8be placed in argon gas or nitrogen, 800 DEG C of heating 24h, obtain the niobates LiNb containing Lacking oxygen 3o 7.8.Embodiment 3 is copied to do charge-discharge test.Analog result is in table 1.
embodiment 8
According to Li 0.95nb 3o 8in the proportioning of each element get highly purified Li respectively 2cO 3powder and Nb 2o 5powder adds alcohol and is diluted to white paste; Compressing tablet after Drying and cooling, is warming up to 800 DEG C with the heating rate of 5 DEG C/min in atmosphere, and is incubated 2 hours, can obtain required niobates Li 0.95nb 3o 8.Copy embodiment 3 to do charge-discharge test, analog result is in table 1.
embodiment 9
According to LiTi 0.05nb 2.95o 8in the proportioning of each element get highly purified Li respectively 2cO 3powder, Nb 2o 5powder and TiO 2powder adds alcohol and is diluted to white paste; Compressing tablet after Drying and cooling, is warming up to 800 DEG C with the heating rate of 5 DEG C/min in atmosphere, and is incubated 2 hours, can obtain required niobates LiTi 0.05nb 2.95o 8.Embodiment 3 is copied to do charge-discharge test.Analog result is in table 1.
embodiment 10
By Nb (OH) 5citric acid is dissolved in, by LiTi at 80 DEG C 0.05nb 2.95o 8stoichiometric proportion adds LiNO 3powder and TiCl 4liquid, treats LiNO 3and TiCl 4after dissolving completely, continuous heating, forms colloidal sol, by colloidal sol as in baking oven, finally forms gel, gel is transferred to Al 2o 3in crucible, then heat in atmosphere, temperature at 600 DEG C, and obtains nanometer LiTi after being incubated 2 hours 0.05nb 2.95o 8.Copy embodiment 3 to do charge-discharge test, analog result is in table 1.
embodiment 11
According to LiTi 0.05nb 2.95o 8in the proportioning of each element get highly purified Li respectively 2cO 3powder, Nb 2o 5powder and TiO 2powder adds alcohol and is diluted to white paste; After Drying and cooling, compressing tablet in atmosphere, is warming up to 800 DEG C with the heating rate of 5 DEG C/min, and be incubated 2 hours, can obtain required niobates LiTi 0.05nb 2.95o 8.
By the LiTi prepared 0.05nb 2.95o 8after powder and ionic liquid [EMIm] [N (CN) 2] (1-ethyl-3-methy limidazolium dicyanamide) Homogeneous phase mixing in an inert atmosphere 600 DEG C heat 4h, obtain the niobates composite material that C is coated after cooling: C-LiTi 0.05nb 2.95o 8.Copy embodiment 3 to do charge-discharge test, analog result is in table 1.
embodiment 12
According to NaNb 3o 8in the proportioning of each element get highly purified Na respectively 2cO 3powder and Nb 2o 5powder adds alcohol and is diluted to white paste; After Drying and cooling, compressing tablet is warming up to 1000 DEG C with the heating rate of 5 DEG C/min in atmosphere, and obtains NaNb after being incubated 2 hours 3o 8.Copy embodiment 3 to do charge-discharge test, analog result is in table 1.
embodiment 13
According to Li 0.1k0.9Nb 3o 8in the proportioning of each element get highly purified Li respectively 2cO 3, K 2cO 3powder and Nb 2o 5powder adds alcohol and is diluted to white paste; Drying and cooling sheet is warming up to 900 DEG C with the heating rate of 5 DEG C/min in atmosphere, and obtains Li after being incubated 2 hours 0.1k 0.9nb 3o 8.Copy embodiment 3 to do charge-discharge test, analog result is in table 1.
embodiment 14
According to Na 0.8k 0.2nb 3o 8in the proportioning of each element get highly purified Na respectively 2cO 3, K 2cO 3powder and Nb 2o 5powder adds alcohol and is diluted to white paste; Compressing tablet after Drying and cooling, is warming up to 900 DEG C with the heating rate of 5 DEG C/min in atmosphere, and obtains Na after being incubated 2 hours 0.8k 0.2nb 3o 8.Copy embodiment 3 to do charge-discharge test, analog result is in table 1.
embodiment 15
By Nb (OH) 5citric acid is dissolved in, by KNb at 80 DEG C 3o 8stoichiometric proportion adds KNO 3powder liquid, treats KNO 3after dissolving completely, continuous heating, forms colloidal sol, by colloidal sol as in baking oven, finally forms gel, gel is transferred to Al 2o 3in crucible, then heat in atmosphere, temperature at 700 DEG C, and obtains nanometer KNb after being incubated 2 hours 3o 8.Copy embodiment 3 to do charge-discharge test, analog result is in table 1.
embodiment 16
According to Li 0.95na 0.05b 0.1nb 2.9o 8in the proportioning of each element get highly purified Li respectively 2cO 3powder, Na 2cO 3powder, B 2o 3powder and Nb 2o 5powder adds alcohol and is diluted to white paste; Compressing tablet after Drying and cooling, is warming up to 800 DEG C with the heating rate of 5 DEG C/min in atmosphere, and is incubated 2 hours, can obtain required Li 0.95na 0.05b 0.1nb 2.9o 8.
By the Li prepared 0.95na 0.05b 0.1nb 2.9o 8with after glucose Homogeneous phase mixing in an inert atmosphere 700 DEG C heat 4h, obtain the niobates composite material that carbon is coated after cooling: C-Li 0.95na 0.05b 0.1nb 2.9o 8.Copy embodiment 3 to do charge-discharge test, analog result is in table 1.
Table 1, the head week charge-discharge test result of the niobates negative material of various form.
Embodiment Material Specific discharge capacity Charge specific capacity
6 LiNb 3O 7.9 248 173
7 LiNb 3O 7.8 252 168
8 Li 0.95Nb 3O 8 262 177
9 LiTi 0.05Nb 2.95O 8 265 181
10 Nano-LiTi 0.05Nb 2.95O 8 275 241
11 C-LiTi 0.05Nb 2.95O 8 284 247
12 NaNb 3O 8 242 164
13 Li 0.1K 0.9Nb 3O 8 246 168
14 Na 0.8K 0.2Nb 3O 8 240 161
15 Nano-KNb 3O 8 259 196
16 C-Li 0.95Na 0.05B 0.1Nb 2.9O 8 282 244

Claims (18)

1. there is the application of niobates in the negative material preparing serondary lithium battery for following general formula,
Niobates general formula: L am bnb co d,
L is selected from one or more of Li, Na or K;
M is selected from one or more in B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, Ta;
A, b, c, d represent molar percentage, 0.8≤a≤1.1,0 ﹤ b ﹤ 0.2,2.9≤c≤3.1,7.8≤d≤8.
2. application according to claim 1, is characterized in that: the preparation method of described niobates comprises the steps:
By L source, M source and Nb 2o 5powder is according to L am bnb co dafter molar ratio ingredient, add solvent dilution and become white paste; Above-mentioned pastel is dry under a little more than the environment of room temperature after ball milling, and after cooling, compressing tablet is white plates; Above-mentioned white plates is placed in Al 2o 3in crucible, then Fast Heating in atmosphere, temperature between 700-1000 DEG C, and obtains L after being incubated a few hours am bnb co d.
3. application according to claim 2, is characterized in that: L source is containing the material containing Li, Na or K oxide after Li, Na or K or decomposes.
4. application according to claim 2, is characterized in that: M source is containing the material containing B, Al, Ti, V, Cr, Mn, Fe, Co or Ni oxide after B, Al, Ti, V, Cr, Mn, Fe, Co or Ni or decomposes.
5. application according to claim 1, is characterized in that: the preparation method of described niobates comprises the steps:
By Nb (OH) 5aqueous citric acid solution is dissolved in, according to L at 80 DEG C am bnb co din the proportioning of each element, after L source and M source are added batching, continuous heating, forms colloidal sol, colloidal sol is placed in baking oven, finally forms gel, gel is transferred to Al 2o 3in crucible, then heat in atmosphere, temperature between 500-700 DEG C, and is incubated a few hours, obtains nano level L after cooling am bnb co d.
6. application according to claim 5, is characterized in that: L source is containing the material containing Li, Na or K oxide after Li, Na or K or decomposes.
7. application according to claim 5, is characterized in that: M source is containing the material containing B, Al, Ti, V, Cr, Mn, Fe, Co or Ni oxide after B, Al, Ti, V, Cr, Mn, Fe, Co or Ni or decomposes.
8. a niobates composite material, has following general formula: C-L am bnb co d,
C is carbon, and described carbon is coated on niobates L am bnb co dthe surface of particle;
L is selected from one or more of Li, Na or K;
M is selected from one or more in B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, Ta;
A, b, c, d represent molar percentage, 0.8≤a≤1.1,0 ﹤ b ﹤ 0.2,2.9≤c≤3.1,7.8≤d≤8.
9. niobates composite material according to claim 8, is characterized in that: the mass percentage of described carbon is less than or equal to 20% for being greater than zero.
10. niobates composite material according to claim 8, is characterized in that: the mass percentage of described carbon is 0.1%-10%.
Niobates composite material according to any one of 11. according to Claim 8 to 10, is characterized in that: by described niobates L am bnb co dcarry out the coated process of carbon, comprise the steps:
By described niobates L am bnb co dwith containing after carbon compound Homogeneous phase mixing in an inert atmosphere 400 ~ 800 DEG C heat a few hours, fully after reaction, after cooling, obtain niobates composite material.
12. niobates composite materials according to claim 11, is characterized in that: described containing carbon compound to be heating-up temperature interval the be organic compound of 400 ~ 700 DEG C.
13. niobates composite materials according to claim 12, is characterized in that: described organic compound is sucrose, glucose or ionic liquid.
14. niobates composite materials according to claim 13, is characterized in that: described ionic liquid is [EMIm] [N (CN) 2].
In 15. claims 8 to 14, the application of electrode material of serondary lithium battery prepared by arbitrary described niobates composite material.
16. application according to claim 15, is characterized in that: described electrode material is negative material.
The negative pole of 17. 1 kinds of serondary lithium batteries, comprises collector and the negative material of load on this collector, and described negative material is described niobates composite material arbitrary in niobates or claim 8 to 14;
Described niobates general formula: L am bnb co d,
L is selected from one or more of Li, Na or K;
M is selected from one or more in B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, Ta;
A, b, c, d represent molar percentage, 0.8≤a≤1.1,0 ﹤ b ﹤ 0.2,2.9≤c≤3.1,7.8≤d≤8.
18. 1 kinds of serondary lithium batteries, comprise positive pole, negative pole and electrolyte, and described negative pole is negative pole according to claim 17.
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