CN102760876A - 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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CN102760876A
CN102760876A CN2011101120416A CN201110112041A CN102760876A CN 102760876 A CN102760876 A CN 102760876A CN 2011101120416 A CN2011101120416 A CN 2011101120416A CN 201110112041 A CN201110112041 A CN 201110112041A CN 102760876 A CN102760876 A CN 102760876A
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niobates
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composite material
niobate
lithium battery
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CN102760876B (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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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 thereof and its application in serondary lithium battery, in particular to niobates and composite material, its preparation method and contain the negative pole and the battery of this material and composite material.
Background technology
(Acta Chemica Scandinavica., 25, (1971) 3337 in early days; Journal of Crystal Growth.18, (1973) 179-184; Journal of the European Ceramic Society., 26, (2006) 2031-2034) to LiNb 3O 8The research preparation, structure that concentrate on its material with and application aspect ceramic.S.O.Yoon, J.H.Yoon, et al is with high-purity Li 2CO 3Powder and Nb 2O 5Fire 700-850 ℃ after the powder and obtain LiNb 3O 8, then with TiO 2Burn till fine and close pottery at 1200-1350 ℃, can be used as ceramic material and use.
M.Anji Reddy delivered " Facile insertion of lithium into nanocrystalline AlNbO in 2008 on the Chem.Mater. magazine 4At room temperature " article, provided nanometer AlNbO 4Has better electrochemical activation.The Goodenough professor had delivered " New Anode Framework for Rechargeable Lithium Batteries " at Chemistry of Materials in 2011, the TiNb that carbon coats 2O 7Discharging and recharging in the interval of 2.5～1.0V, show good performance.The application of niobium base oxide aspect battery obtained broad research.This with market on business-like a kind of lithium cell cathode material lithium titanate (Li 4Ti 5O 12) compare bigger energy storage advantage is arranged; The theoretical capacity of lithium titanate is greatly about 175mAh/g, though lithium titanate has better cycle performance, itself electronic conductance is not high; Need relevant modification to handle the electricity that could improve it and lead, and its theoretical capacity is on the low side.
Nb in the niobates 5+/ Nb 4+And Nb 4+/ Nb 3+ oxidation-reduction pair between 1～3V, can realize 2 electron transfers, therefore have very high theoretical capacity.But material as the broad stopband; The electronic conductance of niobates is also bad, in practical application, requires the niobates electrode material to have higher electronic conductance and ionic conductance simultaneously; Stability of structure; And good electrical conductivity between the maintenance electrode material, stable crystal boundary and smaller volume deformation also will be arranged, and ion transport is unobstructed.
Summary of the invention
In order to overcome above-mentioned defective, an object of the present invention is to provide the application of a kind of niobates electrode material in the preparation serondary lithium battery, the preferably application 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 among B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, the Ta;
A, b, c, d represents molar percentage, 0.8≤a≤1.1,0≤b＜0.2,2.9≤c≤3.1,7.8≤d≤8.
7.8 the situation that the aerobic room exists can be represented in≤d≤8, the cation of available low price substitutes Nb.
Wherein, in the specific embodiments, niobates is to be got by the solid phase method preparation, and this method comprises the steps:
With L source, M source and Nb 2O 5Powder is according to L aM bNb cO dBehind the molar ratio ingredient, add solvent dilution and become white paste; Above-mentioned pastel is through dry under a little more than the environment of room temperature behind the ball milling, cooling back compressing tablet.With above-mentioned white plates as for Al 2O 3In the crucible, Fast Heating in air then, temperature and obtain L after being incubated several hours between 700-1000 ℃ aM bNb cO d
Further above-mentioned L aM bNb cO dPlace argon gas or nitrogen, 700-800 ℃ is heated 5-24h, obtains containing the niobates in aerobic room.
Wherein, further in the specific embodiments, niobates is by following method preparation:
With Nb (OH) 5Under 80 ℃, be dissolved in aqueous citric acid solution, according to L aM bNb cO dIn the proportioning of each element, L source and M source added batching after, continue heating, form colloidal sol, colloidal sol as in the baking oven, is finally formed gel, gel is transferred to Al 2O 3In the crucible, in air, heat then, temperature and is incubated several hours between 500-700 ℃, obtain nano level L after the cooling aM bNb cO d
Preferably, the L source is to contain the material that contains Li, Na or K oxide after Li, Na or K or the decomposes.
Preferably, the M source is to contain the material that contains B, Al, Ti, V, Cr, Mn, Fe, Co or Ni oxide after B, Al, Ti, V, Cr, Mn, Fe, Co or Ni or the decomposes.
Of the present invention have a purpose 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 a carbon, and said 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 among B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, the Ta;
A, b, c, d represents molar percentage, 0.8≤a≤1.1,0≤b＜0.2,2.9≤c≤3.1,7.8≤d≤8.
7.8 the situation that the aerobic room exists can be represented in≤d≤8, concrete operations can use cation (Ti, Mn etc.) at a low price to substitute Nb.
The quality percentage composition of said carbon is greater than zero smaller or equal to 20%, is preferably 0.1%-10%.
Wherein, in the specific embodiments, niobates is to be got by the solid phase method preparation, and this method comprises the steps:
With L source, M source and Nb 2O 5Powder is according to L aM bNb cO dBehind the molar ratio ingredient, add solvent dilution and become white paste; Above-mentioned pastel is through dry under a little more than the environment of room temperature behind the ball milling, cooling back compressing tablet.With above-mentioned white plates as for Al 2O 3In the crucible, Fast Heating in air then, temperature and obtain L after being incubated several hours between 700-1000 ℃ aM bNb cO d
Further above-mentioned L aM bNb cO dPlace argon gas or nitrogen, 700-800 ℃ is heated 5-24h, obtains containing the niobates in aerobic room.
Wherein, further in the specific embodiments, niobates is by following method preparation:
With Nb (OH) 5Under 80 ℃, be dissolved in aqueous citric acid solution, according to L aM bNb cO dIn the proportioning of each element, L source and M source added batching after, continue heating, form colloidal sol, colloidal sol as in the baking oven, is finally formed gel, gel is transferred to Al 2O 3In the crucible, in air, heat then, temperature and is incubated several hours between 500-700 ℃, obtain nano level L after the cooling aM bNb cO d
Preferably, the L source is to contain the material that contains Li, Na or K oxide after Li, Na or K or the decomposes.
Preferably, the M source is to contain the material that contains B, Al, Ti, V, Cr, Mn, Fe, Co or Ni oxide after B, Al, Ti, V, Cr, Mn, Fe, Co or Ni or the decomposes.
Wherein, carrying out the method that carbon coat to handle comprises the steps:
With said niobates with contain carbon compound and evenly mix back 400～800 ℃ of heating a few hours under inert gas environment, fully after the reaction, obtain the niobates composite after the cooling.
Wherein, the said carbon compound that contains is that the heating-up temperature interval is 400～700 ℃ a organic compound.Preferably sucrose, glucose or ionic liquid, preferred [the EMIm] [N (CN) of ionic liquid 2].
A further object of the present invention provides the application of a kind of niobates composite material at the electrode material of preparation serondary lithium battery.
The electrode material of above-mentioned serondary lithium battery is like negative material.
A further object of the present invention provides a kind of secondary lithium battery cathode.
Particularly, this negative pole comprises collector and loads on the negative material on this collector that said negative material is above-mentioned niobates and composite material thereof.
Wherein, collector can adopt the known common negative current collector of this field of batteries, and there is no particular limitation.
Further object of the present invention provides a kind of lithium battery, and this battery comprises positive pole, negative pole and electrolyte, and said negative pole is the above-mentioned negative pole that contains 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 devices, for example can be applied to portable energy-storing equipment, electric automobile and electric tool, back-up source, redundant electrical power, be not limited to this as the above-mentioned serondary lithium battery of negative pole.
Compared with prior art, the present invention possesses following beneficial effect at least:
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 up to 283mAh/g, and can be good at circulation as its first 0-3V voltage inner capacities that discharges and recharges in week of the negative pole of secondary lithium battery; Behind the ball milling, evenly mix, in the 1-3V voltage range with material with carbon element; Reversible capacity can reach more than the 210mAh/g, and capacity can be stabilized in more than the 180mAh/g, be better than market on lithium titanate material; Capacity is 160mAh/g, is one of potential material that replaces lithium titanate.
3, contain the negative material that niobates of the present invention and composite material thereof can be used as lithium ion battery, better cycle performance is arranged, safe, pollution-free, low price, technology is simple, is widely used, and is expected to replace now the lithium titanate (Li of broad research 4Ti 5O 12) material, can be applied to portable energy-storing equipment, electric automobile and electric tool, back-up source, redundant electrical power etc.
4, preparation technology of the present invention is simple, meets modernized large-scale production fully, and great application prospect is arranged.
Description of drawings
Below, specify embodiment of the present invention in conjunction with accompanying drawing, wherein:
Fig. 1 is the X-ray diffractogram of niobates of the present invention;
Fig. 2 be niobates of the present invention in the 0-3V voltage range, current density is the charging and discharging curve of 20mAh/g;
Fig. 3 is the present invention through the niobates that obtains behind the high-energy ball milling in the 1-3V voltage range, and current density is the charging and discharging curve of 20mA/g.
In the 1-3V voltage range, current density is the charge and discharge cycles process of 20mA/g through the niobates that obtains behind the high-energy ball milling in the present invention that Fig. 4 is.
Fig. 5 niobates composite material that to be the present invention obtain after carbon coats is in the 1-3V voltage range, and 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 the 1-3V voltage range, current density is the charging and discharging curve of 20mA/g.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention., these embodiment are not used in restriction scope of the present invention but only limiting to the present invention is described.
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; Oven dry cooling back compressing tablet, the heating rate with 5 ℃/min in air is warming up to 800 ℃, and obtains pure sample after being incubated 2 hours.Fig. 1 has provided pure phase LiNb 3O 8The XRD 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; Oven dry cooling back compressing tablet heating rate with 5 ℃/min in air is warming up to 800 ℃, and is incubated 2 hours, can obtain required niobates LiNb 3O 8
According to LiNb 3O 8, acetylene black, PVDF respectively accounts for 80%, 10%, 10% proportioning and is prepared into electrode, as an electrode of half-cell, to the electrodes use lithium metal, with the LiPF of 1mol/L 6(EC-divinyl carbonic ester (DEC) (volume ratio of EC and DEC 1: 1) is assembled into battery and its battery is carried out charge-discharge test as electrolyte/vinyl carbonate in glove box.Voltage range is at 0-3V, and current density is 20mA/g, and test result is seen 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; Oven dry cooling back compressing tablet, the heating rate with 5 ℃/min in air is warming up to 800 ℃, and is incubated and obtains required niobates LiNb after 2 hours 3O 8With obtaining the particle below the 100nm after the high-energy ball milling of the sample that obtains through 24h.Copy embodiment 2 to do charge-discharge test.Voltage range is at 1-3V, and current density is 20mA/g, and test result is seen 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; Oven dry cooling back compressing tablet, the heating rate with 5 ℃/min in air is warming up to 800 ℃, and is incubated 2 hours, can obtain required niobates LiNb 3O 8
With the LiNb for preparing 3O 8Powder evenly mixes back 700 ℃ of heating 4h under inert gas environment with sucrose, obtains the niobates composite material that C coats: C-LiNb after the cooling 3O 8Copy embodiment 3 to do charge-discharge test, test result is seen Fig. 5.
Embodiment 5
With Nb (OH) 5Under 80 ℃, being dissolved in citric acid, is n (Li)/n (Nb)=1: 3 adding LiNO in molar ratio 3Powder, treat that LiNO3 dissolves fully after, continue heating, form colloidal sol, colloidal sol as in the baking oven, is finally formed gel, gel is transferred to Al 2O 3In the crucible, in air, heat then, temperature is at 600 ℃, and is incubated and obtains required nanometer niobates LiNb after 2 hours 3O 8Copy embodiment 3 to do charge-discharge test, test result is seen 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; The oven dry cooling fin, the heating rate with 5 ℃/min in air is warming up to 800 ℃, and is incubated 2 hours, can obtain the niobates LiNb of required pure sample 3O 8Material.
With the LiNb for preparing 3O 8Place argon gas or nitrogen, 700 ℃ are heated 5h, obtain containing the niobates LiNb in aerobic room 3O 7.9Copy embodiment 3 to do charge-discharge test, analog result is seen 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; Oven dry cooling back compressing tablet, the heating rate with 5 ℃/min in air is warming up to 800 ℃, and is incubated 2 hours, can obtain the niobates LiNb of required pure sample 3O 8
With the LiNb for preparing 3O 8Place argon gas or nitrogen, 800 ℃ are heated 24h, obtain containing the niobates LiNb in aerobic room 3O 7.8Copy embodiment 3 to do charge-discharge test.Analog result is seen 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; Oven dry cooling back compressing tablet, the heating rate with 5 ℃/min in air is warming up to 800 ℃, and is incubated 2 hours, can obtain required niobates Li 0.95Nb 3O 8Copy embodiment 3 to do charge-discharge test, analog result is seen 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; Oven dry cooling back compressing tablet, the heating rate with 5 ℃/min in air is warming up to 800 ℃, and is incubated 2 hours, can obtain required niobates LiTi 0.05Nb 2.95O 8Copy embodiment 3 to do charge-discharge test.Analog result is seen table 1.
Embodiment 10
With Nb (OH) 5Under 80 ℃, be dissolved in citric acid, press LiTi 0.05Nb 2.95O 8Stoichiometric proportion adds LiNO 3Powder and TiCl 4Liquid is treated LiNO 3And TiCl 4After the dissolving, continue heating fully, form colloidal sol, colloidal sol as in the baking oven, is finally formed gel, gel is transferred to Al 2O 3In the crucible, in air, heat then, temperature is at 600 ℃, and obtains nanometer LiTi after being incubated 2 hours 0.05Nb 2.95O 8Copy embodiment 3 to do charge-discharge test, analog result is seen 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; Oven dry cooling back compressing tablet is warming up to 800 ℃ with the heating rate of 5 ℃/min, and is incubated 2 hours in air, can obtain required niobates LiTi 0.05Nb 2.95O 8
With the LiTi for preparing 0.05Nb 2.95O 8Powder evenly mixes back 600 ℃ of heating 4h under inert gas environment with ionic liquid [EMIm] [N (CN) 2] (1-ethyl-3-methy limidazolium dicyanamide), obtains the niobates composite material that C coats: C-LiTi after the cooling 0.05Nb 2.95O 8Copy embodiment 3 to do charge-discharge test, analog result is seen 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; Oven dry cooling back compressing tablet heating rate with 5 ℃/min in air is warming up to 1000 ℃, and obtains NaNb after being incubated 2 hours 3O 8Copy embodiment 3 to do charge-discharge test, analog result is seen 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; Oven dry cooling fin heating rate with 5 ℃/min in air is warming up to 900 ℃, and obtains Li after being incubated 2 hours 0.1K 0.9Nb 3O 8Copy embodiment 3 to do charge-discharge test, analog result is seen 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; Oven dry cooling back compressing tablet, the heating rate with 5 ℃/min in air is warming up to 900 ℃, and obtains Na after being incubated 2 hours 0.8K 0.2Nb 3O 8Copy embodiment 3 to do charge-discharge test, analog result is seen table 1.
Embodiment 15
With Nb (OH) 5Under 80 ℃, be dissolved in citric acid, press KNb 3O 8Stoichiometric proportion adds KNO 3Powder liquid is treated KNO 3After the dissolving, continue heating fully, form colloidal sol, colloidal sol as in the baking oven, is finally formed gel, gel is transferred to Al 2O 3In the crucible, in air, heat then, temperature is at 700 ℃, and obtains nanometer KNb after being incubated 2 hours 3O 8Copy embodiment 3 to do charge-discharge test, analog result is seen 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; Oven dry cooling back compressing tablet, the heating rate with 5 ℃/min in air is warming up to 800 ℃, and is incubated 2 hours, can obtain required Li 0.95Na 0.05B 0.1Nb 2.9O 8
With the Li for preparing 0.95Na 0.05B 0.1Nb 2.9O 8Evenly mix back 700 ℃ of heating 4h under inert gas environment with glucose, obtain the niobates composite material that carbon coats: C-Li after the cooling 0.95Na 0.05B 0.1Nb 2.9O 8Copy embodiment 3 to do charge-discharge test, analog result is seen table 1.
Table 1, first all charge-discharge test results of the niobates negative material of various forms.
Embodiment Material Specific discharge capacity The charge ratio 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 (9)

1. the application of niobates in the electrode material of preparation serondary lithium battery with following general formula, the preferably application in negative material;
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 among B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, the Ta;
A, b, c, d represents 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 said niobates comprises the steps:
With L source, M source and Nb 2O 5Powder is according to L aM bNb cO dBehind the molar ratio ingredient, add solvent dilution and become white paste; Above-mentioned pastel is through dry under a little more than the environment of room temperature behind the ball milling, cooling back compressing tablet; With above-mentioned white plates as for Al 2O 3In the crucible, Fast Heating in air then, temperature and obtain L after being incubated several hours between 700-1000 ℃ aM bNb cO d
Preferably, the L source is to contain the material that contains Li, Na or K oxide after Li, Na or K or the decomposes.
Preferably, the M source is to contain the material that contains B, Al, Ti, V, Cr, Mn, Fe, Co or Ni oxide after B, Al, Ti, V, Cr, Mn, Fe, Co or Ni or the decomposes.
3. application according to claim 1 is characterized in that: the preparation method of said niobates comprises the steps:
With Nb (OH) 5Under 80 ℃, be dissolved in aqueous citric acid solution, according to L aM bNb cO dIn the proportioning of each element, L source and M source added batching after, continue heating, form colloidal sol, colloidal sol as in the baking oven, is finally formed gel, gel is transferred to Al 2O 3In the crucible, in air, heat then, temperature and is incubated several hours between 500-700 ℃, obtain nano level L after the cooling aM bNb cO d
Preferably, the L source is to contain the material that contains Li, Na or K oxide after Li, Na or K or the decomposes.
Preferably, the M source is to contain the material that contains B, Al, Ti, V, Cr, Mn, Fe, Co or Ni oxide after B, Al, Ti, V, Cr, Mn, Fe, Co or Ni or the decomposes.
4. a niobates composite material has following general formula: C-L aM bNb cO d,
C is a carbon, and said 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 among B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, the Ta;
A, b, c, d represents molar percentage, 0.8≤a≤1.1,0≤b＜0.2,2.9≤c≤3.1,7.8≤d≤8.
Preferably, the quality percentage composition of said carbon is greater than zero smaller or equal to 20%, more preferably 0.1%-10%.
5. niobates composite material according to claim 4 is characterized in that: with said niobates L aM bNb cO dCarry out carbon and coat processing, comprise the steps:
With said niobates L aM bNb cO dWith contain carbon compound and evenly mix back 400～800 ℃ of heating several hours under inert gas environment, fully after the reaction, obtain the niobates composite material after the cooling.
6. niobates composite material according to claim 5 is characterized in that: the said carbon compound that contains is that the heating-up temperature interval is 400～700 ℃ a organic compound, preferably sucrose, glucose or ionic liquid, preferred [the EMIm] [N (CN) of ionic liquid 2].
7. claim 5 or 6 arbitrary described niobates composite materials are preferably negative material in the application of the electrode material of preparation serondary lithium battery.
8. a secondary lithium battery cathode comprises collector and loads on the negative material on this collector, and said negative material is niobates or claim 5 or 6 described niobates composite materials;
Said 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 among B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, the Ta;
A, b, c, d represents molar percentage, 0.8≤a≤1.1,0≤b＜0.2,2.9≤c≤3.1,7.8≤d≤8.
9. a serondary lithium battery comprises positive pole, negative pole and electrolyte, and said negative pole is the described negative pole of claim 8.
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105322143A (en) * 2014-07-04 2016-02-10 中信国安盟固利动力科技有限公司 Nano microsphere niobium-based composite oxide and preparation method thereof
JP2016054051A (en) * 2014-09-03 2016-04-14 トヨタ自動車株式会社 Negative electrode active material for sodium ion battery, and sodium ion battery
JP5915812B2 (en) * 2013-08-07 2016-05-11 トヨタ自動車株式会社 Negative electrode active material for sodium ion battery and sodium ion battery
CN106848213A (en) * 2015-12-04 2017-06-13 丰田自动车株式会社 The manufacture method of active agent complex
CN107742716A (en) * 2017-10-12 2018-02-27 海南大学 A kind of electrode material of lithium ion battery and preparation method thereof
CN109119630A (en) * 2018-08-30 2019-01-01 陕西科技大学 A kind of niobic acid tin is nanocrystalline and preparation method thereof and is preparing the application in lithium battery
CN109638259A (en) * 2018-12-18 2019-04-16 中科廊坊过程工程研究院 A kind of complex ternary positive electrode and preparation method thereof
CN109671946A (en) * 2018-12-17 2019-04-23 深圳先进技术研究院 Zinc ion battery positive electrode active materials, positive electrode, Zinc ion battery anode, Zinc ion battery and its preparation method and application
CN109802130A (en) * 2018-12-24 2019-05-24 肇庆市华师大光电产业研究院 A kind of lithium ion one-shot battery nanometer anode material and preparation method thereof
CN110002875A (en) * 2019-05-09 2019-07-12 南昌航空大学 A method of utilizing tantalum modified sodium niobate-calcium zirconate based antiferroelectric ceramics energy storage
CN110148741A (en) * 2019-06-20 2019-08-20 山东大学 A kind of cladded type molybdic acid niobium lithium material and the preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1597613A (en) * 2004-08-06 2005-03-23 哈尔滨工业大学 Method of preparing lithium niobate nanometer powder at low-temp by citric acid gel method
CN101232095A (en) * 2008-02-02 2008-07-30 广州市鹏辉电池有限公司 Lithium ion battery positive pole active materials and battery
CN101807688A (en) * 2010-04-26 2010-08-18 安徽工业大学 Niobium-doped lithium titanate anode material for lithium ion battery and method for preparing same
CN101807696A (en) * 2010-04-12 2010-08-18 浙江大学 Titanium phosphate lithium material used for cathode of lithium ion battery and preparation method thereof
JP2010248044A (en) * 2009-04-17 2010-11-04 Sumitomo Electric Ind Ltd LiNbO3 GLASS, METHOD FOR PRODUCING THE SAME AND NONAQUEOUS ELECTROLYTE CELL USING LiNbO3 GLASS

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1597613A (en) * 2004-08-06 2005-03-23 哈尔滨工业大学 Method of preparing lithium niobate nanometer powder at low-temp by citric acid gel method
CN101232095A (en) * 2008-02-02 2008-07-30 广州市鹏辉电池有限公司 Lithium ion battery positive pole active materials and battery
JP2010248044A (en) * 2009-04-17 2010-11-04 Sumitomo Electric Ind Ltd LiNbO3 GLASS, METHOD FOR PRODUCING THE SAME AND NONAQUEOUS ELECTROLYTE CELL USING LiNbO3 GLASS
CN101807696A (en) * 2010-04-12 2010-08-18 浙江大学 Titanium phosphate lithium material used for cathode of lithium ion battery and preparation method thereof
CN101807688A (en) * 2010-04-26 2010-08-18 安徽工业大学 Niobium-doped lithium titanate anode material for lithium ion battery and method for preparing same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JIAN-TAO HAN等: ""Lithium Ion Intercalation Performance of Niobium", 《CHEM. MATER》, vol. 20, no. 21, 22 September 2009 (2009-09-22), pages 4753 - 4755 *
JIAN-TAO HAN等: ""Lithium Ion Intercalation Performance of Niobium"", 《CHEM. MATER》, vol. 20, no. 21, 22 September 2009 (2009-09-22), pages 4753 - 4755 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5915812B2 (en) * 2013-08-07 2016-05-11 トヨタ自動車株式会社 Negative electrode active material for sodium ion battery and sodium ion battery
CN105322143B (en) * 2014-07-04 2018-03-20 中信国安盟固利动力科技有限公司 A kind of nanoparticle niobium base composite oxidate and preparation method thereof
CN105322143A (en) * 2014-07-04 2016-02-10 中信国安盟固利动力科技有限公司 Nano microsphere niobium-based composite oxide and preparation method thereof
JP2016054051A (en) * 2014-09-03 2016-04-14 トヨタ自動車株式会社 Negative electrode active material for sodium ion battery, and sodium ion battery
CN106848213A (en) * 2015-12-04 2017-06-13 丰田自动车株式会社 The manufacture method of active agent complex
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CN109119630B (en) * 2018-08-30 2021-08-13 陕西科技大学 Tin niobate nanocrystal, preparation method thereof and application thereof in preparation of lithium battery
CN109671946A (en) * 2018-12-17 2019-04-23 深圳先进技术研究院 Zinc ion battery positive electrode active materials, positive electrode, Zinc ion battery anode, Zinc ion battery and its preparation method and application
CN109638259A (en) * 2018-12-18 2019-04-16 中科廊坊过程工程研究院 A kind of complex ternary positive electrode and preparation method thereof
CN109638259B (en) * 2018-12-18 2022-08-05 廊坊绿色工业技术服务中心 Composite ternary cathode material and preparation method thereof
CN109802130A (en) * 2018-12-24 2019-05-24 肇庆市华师大光电产业研究院 A kind of lithium ion one-shot battery nanometer anode material and preparation method thereof
CN110002875A (en) * 2019-05-09 2019-07-12 南昌航空大学 A method of utilizing tantalum modified sodium niobate-calcium zirconate based antiferroelectric ceramics energy storage
CN110148741A (en) * 2019-06-20 2019-08-20 山东大学 A kind of cladded type molybdic acid niobium lithium material and the preparation method and application thereof

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