CN102324510A - Lithium ion battery cathode material - Google Patents

Lithium ion battery cathode material Download PDF

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Publication number
CN102324510A
CN102324510A CN201110281969A CN201110281969A CN102324510A CN 102324510 A CN102324510 A CN 102324510A CN 201110281969 A CN201110281969 A CN 201110281969A CN 201110281969 A CN201110281969 A CN 201110281969A CN 102324510 A CN102324510 A CN 102324510A
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China
Prior art keywords
carbon
lithium ion
ion battery
battery negative
negative material
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CN201110281969A
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Chinese (zh)
Inventor
卢志威
刘兴江
彭庆文
孙文彬
任丽彬
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CETC 18 Research Institute
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CETC 18 Research Institute
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Priority to CN201110281969A priority Critical patent/CN102324510A/en
Publication of CN102324510A publication Critical patent/CN102324510A/en
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a lithium ion battery cathode material. The lithium ion battery cathode material is characterized by being a commonly-ball-milled carbon-coated VB subgroup element oxide, wherein the VB subgroup element comprises niobium (Nb) or tantalum (Ta); carbon is a precursor of the carbon and a carbon material; and the mass ratio of the VB subgroup element oxide to the carbon material to the precursor of carbon is (2-8):(1-2):(1-2). According to the lithium ion battery cathode material disclosed by the invention, the niobium (Nb) or tantalum (Ta) oxide and the carbon material are commonly ball milled, thus the conductive performance and the safe performance of the material are improved. The lithium ion battery cathode material also has the characteristics of high electrochemical reversible capacity of the electrode material and is expected to be a new generation of high-capacity lithium ion battery cathode material.

Description

A kind of lithium ion battery negative material
Technical field
The invention belongs to the lithium ion battery material technical field, especially relate to a kind of lithium ion battery negative material.
Background technology
From the nineties in last century; Sony company uses lamella graphite to replace the metal Li of fail safe extreme difference; Prepared since the lithium rechargeable battery that successfully first kind can be filled, lithium ion battery is because of its high-energy-density, and is pollution-free; Applied range has obtained develop rapidly, has expanded fields such as electric tool, electric automobile to from mobile communication power supply, notebook computer, video camera etc.
At present, Li 4Ti 5O 12As intercalation materials of li ions, in electrochemical process, have the high-lithium ion diffusion rate, advantages such as zero volume rate of change become the negative material of lithium ion battery and ultracapacitor, and its theoretical capacity is 175mAh/g, and the actual cycle capacity is 150～160mAh/g.Reaction has very smooth filling-discharge platform, and the average voltage platform is about 1.5V, surpasses 90% of reaction overall process.Owing to be the zero strain electrode material, embed and take off in the process of embedding at lithium ion, obvious change does not take place in its crystal formation, has only very little pucker & bloat, and crystal structure embeds and deviates from the process highly stablely at lithium ion, so its electrochemistry cycle performance is very good.With respect to carbon negative poles such as graphite, fail safe and reliability also are able to improve greatly.Yet, Li 4Ti 5O 12The electrochemistry capacitance of material is less, is merely 175mAhg -1, its electrochemistry capacitance and energy density all are far smaller than traditional material with carbon element, and electrochemistry removal lithium embedded platform and can produce gases all about 1.5V in a large number in electrochemical reaction, influence the assembling of battery.
Summary of the invention
The present invention for solve the technical problem that exists in the known technology provide a kind of technology simple, conduct electricity very well, good cycling stability, safe a kind of lithium ion battery negative material.
The technical scheme that the present invention takes for the technical problem that exists in the solution known technology is:
A kind of lithium ion battery negative material is characterized in: said material is that the carbon of common ball milling coats VB subgroup element oxide, and said VB subgroup element comprises niobium Nb or tantalum Ta.
The present invention can also adopt following technical scheme:
Said VB subgroup element oxide is Nb 2O 5, NbO 2, Nb 2O 3, Ta 2O 5Or a kind of among the non-stoichiometric NbOx.
Said carbon is the presoma and the material with carbon element of carbon.
Said material with carbon element comprises: Delanium, native graphite or carbon fiber.
The presoma of carbon comprises pitch or carbohydrate.
Said pitch is coal tar pitch.
Said carbohydrate is a kind of in monose, disaccharide or the polysaccharide.
The mass ratio that said carbon coats VB subgroup element oxide is a VB subgroup element oxide: material with carbon element: the presoma of carbon=2-8:1-2:1-2.
Advantage and good effect that the present invention has are:
1, the present invention adopts the material with carbon element of common ball milling to coat niobium Nb or tantalum Ta oxide, and niobium or tantalum pentoxide are as storage lithium active material, and its removal lithium embedded current potential is higher; In cell reaction; Do not relate to the dissolving of lithium and separate out, not only improved the material electric conductivity, also have higher safety performance.
2, the present invention also has the high characteristics of electrochemical reversible capacity of electrode material, is expected to become cathode material for high capacity lithium ion battery of new generation.
Description of drawings
Fig. 1 is the embodiment of the invention 1 sample electrode cycle performance curve and charging and discharging curve figure;
Fig. 2 is Nb 2O 5The electrochemistry cycle performance.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, the following examples of giving an example now, and conjunction with figs. 1-2 specifies as follows:
Preparation process of the present invention comprises:
⑴ take by weighing raw material:
By mass ratio VB subgroup element oxide: material with carbon element: the presoma of carbon=2-8:1-2:1-2 takes by weighing the presoma of VB subgroup element oxide, material with carbon element and carbon; Described VB subgroup element oxide is Nb 2O 5, NbO 2, Nb 2O 3, Ta 2O 5Or a kind of among the non-stoichiometric NbOx; Said material with carbon element comprises: Delanium, native graphite or carbon fiber; The presoma of said carbon comprises pitch or carbohydrate;
⑵ prepare mixture paste:
In ball grinder, according to the ratio of solvent/raw-material summation=2-20ml/g, the presoma of the VB subgroup element oxide, material with carbon element and the carbon that take by weighing among the step ⑴ is dissolved in the solvent, carried out common liquid phase stirring and milling 1-100 hour, form mixture paste; Described solvent is one or more in water, acetone, ethanol, toluene, xylenes, hexane, the cyclohexane;
⑶ prepare the negative material presoma:
Mixture paste among the step ⑵ inserted carry out hour heating of 70-120 ℃, 2-10 in the drying box and detach solvent, obtain the negative material presoma;
⑷ prepare lithium ion battery negative material:
The negative material presoma for preparing among the step ⑶ is placed the high temperature furnace under the inert atmosphere; Be warmed up to 500-1200 ℃ with speed 1-10 ℃/min, high temperature sintering 3-24h, powered-down; Behind the natural cooling, obtain coating VB subgroup element oxide material as the carbon of lithium ion battery negative material; Described inert atmosphere is a kind of in the mist of nitrogen or argon gas and hydrogen of nitrogen, argon gas, arbitrary proportion.
Embodiment 1
With 10g Nb 2O 5, 2.5g Delanium, 2.5g coal tar pitch place the ball grinder of 50ml alcohol solvent to carry out common liquid phase stirring and milling 30 hours, form mixture paste; With mixture paste insert carry out in the drying box 80 ℃, 4 hours the heating detach solvent, obtain the negative material presoma; Gained negative material presoma is placed high temperature furnace; Be warmed up to 700 ℃ with 5 ℃/min under the argon gas atmosphere, high temperature sintering 5h, powered-down; Behind the natural cooling; Obtain coating VB subgroup element oxide material as the carbon of lithium ion battery negative material, through performance test, electrode cycle performance curve and charging and discharging curve figure are as shown in Figure 1.
Embodiment 2
With 12g Nb 2O 5, 1.5 coal tar pitch, 1.5g native graphite place the ball grinder of 50ml alcohol solvent to carry out common liquid phase stirring and milling 30 hours, form mixture paste; With mixture paste insert carry out in the drying box 80 ℃, 4 hours the heating detach solvent, obtain the negative material presoma; Gained negative material presoma is placed high temperature furnace, and the following 5 ℃/min of nitrogen atmosphere is warmed up to 700 ℃, high temperature sintering 5h, and powered-down behind the natural cooling, obtains coating VB subgroup element oxide material as the carbon of lithium ion battery negative material.
Comparative example 1
Use TiO 2And Li 2CO 3Under high temperature (850～1000 ℃), synthesize Li 4Ti 5O 12, the time is 24h.In order to compensate Li at high temperature 2CO 3Volatilization, make Li usually 2CO 3Excessive about 8%.
Comparative example 2
With Nb 2O 5Material directly prepares electrode material, tests Nb 2O 5The electrochemistry cycle performance as shown in Figure 2.
The negative material performance that table 1 has been listed different embodiment and comparative example compares.
The comparison of negative material capacity in different embodiment of table 1 and the comparative example
? Embodiment 1 Embodiment 2 Comparative example 1 Comparative example 2
Specific capacity 260mAh/g 260mAh/g 150mAh/g 250 mAh/g
From relatively above, the carbon of the present invention's preparation coats the electrochemistry capacitance of VB subgroup element oxide lithium ion battery negative material than Li 4Ti 5O 12Material is greatly improved, the more untreated Nb of cycle performance 2O 5Also be improved.

Claims (8)

1. lithium ion battery negative material is characterized in that: said material is that the carbon of common ball milling coats VB subgroup element oxide, and said VB subgroup element comprises niobium Nb or tantalum Ta.
2. lithium ion battery negative material according to claim 1 is characterized in that: said VB subgroup element oxide is Nb 2O 5, NbO 2, Nb 2O 3, Ta 2O 5Or a kind of among the non-stoichiometric NbOx.
3. lithium ion battery negative material according to claim 1 is characterized in that: said carbon is the presoma and the material with carbon element of carbon.
4. lithium ion battery negative material according to claim 3 is characterized in that: said material with carbon element comprises: Delanium, native graphite or carbon fiber.
5. lithium ion battery negative material according to claim 3 is characterized in that: the presoma of carbon comprises pitch or carbohydrate.
6. lithium ion battery negative material according to claim 5 is characterized in that: said pitch is coal tar pitch.
7. lithium ion battery negative material according to claim 5 is characterized in that: said carbohydrate is a kind of in monose, disaccharide or the polysaccharide.
8. according to claim 1,2 or 3 described lithium ion battery negative materials, it is characterized in that: the mass ratio that said carbon coats VB subgroup element oxide is a VB subgroup element oxide: material with carbon element: the presoma of carbon=2-8:1-2:1-2.
CN201110281969A 2011-09-21 2011-09-21 Lithium ion battery cathode material Pending CN102324510A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102593441A (en) * 2012-02-27 2012-07-18 中信国安盟固利电源技术有限公司 Synthesizing method of modified columbic anhydride for lithium ion battery
CN106340400A (en) * 2016-09-09 2017-01-18 华中科技大学 Carbon-coating orthorhombic system nanometer rod shape Nb2O5 material and manufacturing method thereof
CN110021744A (en) * 2019-04-18 2019-07-16 中国科学院宁波材料技术与工程研究所 A kind of preparation method of nanometer titanium dioxide niobium/carbon lithium ion cell negative electrode material
CN112086629A (en) * 2020-09-08 2020-12-15 合肥国轩高科动力能源有限公司 Si @ C/ZnNb2O6Preparation method and application of negative electrode composite material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1681145A (en) * 2004-04-05 2005-10-12 中国科学院物理研究所 Negative electrode active material and use of secondary lithium battery
US20060040183A1 (en) * 2004-08-17 2006-02-23 Byd America Corporation Materials for negative electrodes of lithium ion batteries

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1681145A (en) * 2004-04-05 2005-10-12 中国科学院物理研究所 Negative electrode active material and use of secondary lithium battery
US20060040183A1 (en) * 2004-08-17 2006-02-23 Byd America Corporation Materials for negative electrodes of lithium ion batteries

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102593441A (en) * 2012-02-27 2012-07-18 中信国安盟固利电源技术有限公司 Synthesizing method of modified columbic anhydride for lithium ion battery
CN102593441B (en) * 2012-02-27 2017-06-27 中信国安盟固利电源技术有限公司 The synthetic method of modified columbic anhydride for lithium ion battery
CN106340400A (en) * 2016-09-09 2017-01-18 华中科技大学 Carbon-coating orthorhombic system nanometer rod shape Nb2O5 material and manufacturing method thereof
CN106340400B (en) * 2016-09-09 2018-02-23 华中科技大学 A kind of carbon coating rhombic system nano bar-shape Nb2O5Material and preparation method thereof
CN110021744A (en) * 2019-04-18 2019-07-16 中国科学院宁波材料技术与工程研究所 A kind of preparation method of nanometer titanium dioxide niobium/carbon lithium ion cell negative electrode material
CN112086629A (en) * 2020-09-08 2020-12-15 合肥国轩高科动力能源有限公司 Si @ C/ZnNb2O6Preparation method and application of negative electrode composite material
CN112086629B (en) * 2020-09-08 2022-05-06 合肥国轩高科动力能源有限公司 Si @ C/ZnNb2O6Preparation method and application of negative electrode composite material

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Application publication date: 20120118