CN104124452B - A kind of coated lithium iron phosphate positive material of titanium compound and preparation method thereof that conducts electricity - Google Patents
A kind of coated lithium iron phosphate positive material of titanium compound and preparation method thereof that conducts electricity Download PDFInfo
- Publication number
- CN104124452B CN104124452B CN201410354480.1A CN201410354480A CN104124452B CN 104124452 B CN104124452 B CN 104124452B CN 201410354480 A CN201410354480 A CN 201410354480A CN 104124452 B CN104124452 B CN 104124452B
- Authority
- CN
- China
- Prior art keywords
- lifepo4
- titanium
- preparation
- titanium compound
- ethyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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 present invention relates to a kind of coated lithium iron phosphate positive material of titanium compound and preparation method thereof that conducts electricity, be intended to adopt conduction titanium compound as clad, offer electron conduction and the lithium ion conduction characteristic of LiFePO4 excellence. Material of the present invention is nucleocapsid structure, top layer is conduction titanium compound, and core layer is LiFePO4. Preparation method comprises: (1) joins LiFePO4 and titanium source in absolute ethyl alcohol, makes the rear spraying of its hydrolysis dry, then by the powder obtaining roasting cooling with stove under inert gas shielding. (2) powder obtaining in step (1) and reducing agent are joined to ultrasonic dispersion in absolute ethyl alcohol, roasting cooling with stove under inert gas shielding after being dried. (3) powder in crucible is taken out, respectively with absolute ethyl alcohol and deionized water washing, the finally dry end product that obtains in vacuum drying oven. The coated LiFePO4 particle diameter of the method is evenly distributed, and clad conducts electricity very well and can not hinder the conduction of lithium ion, can effectively improve the chemical property of LiFePO4.
Description
Technical field
The present invention relates to adopt the surface coating modification of conduction titanium compound to LiFePO4, belong to field of new.
Background technology
Along with the development of lithium-ion electric pool technology, serondary lithium battery has been widely used in the fields such as electronic product, electric automobile, hybrid vehicle, large-scale power grid and new forms of energy energy storage device. Compared with other anode material of lithium battery, LiFePO4 has high security performance, has extended cycle life, and specific capacity is high, good stability, and aboundresources, cheap, the features such as asepsis environment-protecting, are extensively thought to have one of anode material of lithium battery of development prospect most. In addition, LiFePO4 has good high temperature cyclic performance and does not blast. LiFePO4 is also the splendid positive electrode of large-scale lithium ion battery group, is having larger application space aspect large-sized power battery.
But, have the LiFePO4 of olivine structural self structure characteristics determined in charge and discharge process, lithium ion can only be along<010>conduction of direction one dimension, thereby cause lower electronic conductivity (10-9-10-10S·cm-1). Low electronic conductivity has limited the high-rate charge-discharge capability of ferric phosphate lithium cell, thereby has limited LiFePO4 in the application that requires large electric current fast charging and discharging field. The most frequently used method of head it off is material with carbon-coated surface technology at present. Although the coated battery performance that can improve to a certain extent LiFePO4 of carbon, in actual production, carbon is coated and has a more difficult problem and challenge. For example, in the time that carbon content is lower, can not form complete uniform clad on LiFePO4 surface, can not obtain enough electric conductivities; Along with carbon content increases, clad thickens, and has not only reduced the tap density of active material but also has hindered the diffusion admittance of lithium ion.
Conduction titanium compound is as titanium suboxide (TinO2n-1(1≤n≤20)) or TiB2There is good electric conductivity. And conduction titanium compound has high chemical stability and corrosion resistance, be not easy to decompose, can not affect because producing impurity the carrying out of main reaction as modified material. In addition, the crystal structure of conduction titanium compound has larger space, can allow freely passing through of some ions, can not hinder the diffusion of lithium ion. Due to above performance, conduction titanium compound has very significant effect for ferric phosphate lithium cell material modification.
Summary of the invention
The present invention, according to the chemical stability of conduction titanium compound excellence, good electric conductivity and suitable crystal structure, is coated on LiFePO4 surface, can offer the good electronic conduction ability of LiFePO4. The object of the invention is to be intended to improve the electrical conductivity performance of LiFePO 4 material, to improve its high rate performance and cycle performance.
Above-mentioned purpose of the present invention realizes by following scheme.
First coated by titanium dioxide is formed to stable nucleocapsid structure in LiFePO4 grain surface, wherein core layer is LiFePO4, and top layer is titanium dioxide, then is reduced to conduction titanium compound by reduction reaction.
The coated lithium iron phosphate positive material of conduction titanium compound of gained, is characterized in that: be nucleocapsid structure, top layer is that thickness is the TiB of 5nm ~ 2 μ m2Or titanium suboxide (TinO2n-1(1≤n≤20)) or the two mixture, core layer is LiFePO4, content 60 ~ 99%(mass fraction of LiFePO4).
The preparation method of the coated lithium iron phosphate positive material of conduction titanium compound of the present invention, comprises the steps:
(1) LiFePO4 and titanium source are joined in absolute ethyl alcohol, add subsequently deionized water, whole process all keeps stirring, then spraying is dry, the powder obtaining is placed in to crucible, under inert gas shielding under 600 ~ 750 DEG C of conditions roasting 0.5 ~ 1h, and cooling with stove;
(2) powder obtaining in step (1) and reducing agent are joined to ultrasonic dispersion in absolute ethyl alcohol, dry be placed in crucible under inert gas shielding at 300 ~ 480 DEG C roasting 10 ~ 20 hours, and cooling with stove;
(3) powder in crucible is taken out, with absolute ethyl alcohol and deionized water washing, finally in vacuum drying oven, at 50 ~ 120 DEG C, be dried and obtain end product respectively.
Described in above-mentioned steps (1), titanium source is the one in butyl titanate, tetraethyl titanate, titanium propanolate, titanium tetrachloride, titanyl sulfate, or any several mixture, and the mol ratio in LiFePO4 and titanium source is 1:0.02 ~ 1.3.
Described in above-mentioned steps (2), reducing agent is the one in potassium borohydride, sodium borohydride, or the mixture of the two, and the mol ratio in reducing agent and titanium source is 1:0.2 ~ 0.8.
The coated lithium iron phosphate positive material of conduction titanium compound prepared by the present invention along with the rising of titanium source addition by grey blackening.
Beneficial effect of the present invention is: (1) conduction titanium compound is coated very even to LiFePO4, and to lithium ion, diffusion does not have inhibition; (2) the LiFePO4 electrical conductivity after coated compared with raw-material LiFePO4 increases substantially, and can promote raw-material high rate performance and cycle performance; (3) after adopting this method coated, the tap density of iron phosphate powder raises, and is more conducive to the miniaturization of high-capacity lithium ion cell.
Detailed description of the invention
Embodiment 1
5ml butyl titanate is added in 100ml ethanol and stirs and mix with 46.35g LiFePO4, add subsequently 10ml deionized water, then continue to stir half an hour. Obtained mixed liquor is sprayed to be dried obtains the powder that particle diameter is evenly distributed, and puts into crucible, is placed in the Muffle furnace that passes into argon gas atmosphere with 750 DEG C of roasting 1h, then cooling with stove, obtains the powder of coated by titanium dioxide LiFePO4. Gained powder and 1.53g potassium borohydride are together added in 100ml absolute ethyl alcohol to ultrasonic dispersion 30 minutes, putting into crucible after gained powder for drying, in Muffle furnace, 400 DEG C of roasting 15h, cooling with stove again. Then gained powder is cleaned up repeatedly to last 60 DEG C of vacuum drying with deionized water and ethanol. Can obtain conducting electricity the coated iron phosphate powder of titanium compound.
Embodiment 2
5ml tetraethyl titanate is added in 80ml ethanol and stirs and mix with 34.55g LiFePO4, add subsequently 5ml deionized water, then continue to stir half an hour. Obtained mixed liquor is sprayed to be dried obtains the powder that particle diameter is evenly distributed, and puts into crucible, is placed in the Muffle furnace that passes into argon gas atmosphere with 700 DEG C of roasting 0.5h, then cooling with stove, obtains the iron phosphate powder of coated by titanium dioxide. Again gained powder and 1.04g sodium borohydride are together added in 100ml absolute ethyl alcohol to ultrasonic dispersion 30 minutes, putting into crucible after gained powder for drying, with 370 DEG C of roasting 20h, cooling with stove in Muffle furnace. Then gained powder is cleaned up repeatedly with deionized water and ethanol, finally in 100 DEG C of vacuum drying. Can obtain conducting electricity the coated iron phosphate powder of titanium compound.
Claims (3)
1. conduct electricity the preparation method of the coated lithium iron phosphate positive material of titanium compound, it is characterized in that: this material is nucleocapsid structure, top layer is that thickness is the TiB of 5nm～2 μ m2Or titanium suboxide TinO2n-1, 1≤n≤20, or the mixture of the two, core layer is LiFePO4, the content 60～99% (mass fraction) of LiFePO4, the method comprises the steps: that (1) joins LiFePO4 and titanium source in absolute ethyl alcohol, add subsequently deionized water, whole process all keeps stirring, then spraying is dry, the powder obtaining is placed in to crucible, under inert gas shielding under 600～750 DEG C of conditions roasting 0.5～1h, and cooling with stove, (2) powder obtaining in step (1) and reducing agent are joined to ultrasonic dispersion in absolute ethyl alcohol, dry be placed in crucible under inert gas shielding at 300～480 DEG C roasting 10～20 hours, and cooling with stove, (3) powder in crucible is taken out, respectively with absolute ethyl alcohol and deionized water washing, finally in vacuum drying oven, at 50～120 DEG C, be dried and obtain end product.
2. preparation method according to claim 1, it is characterized in that: described titanium source is the one in butyl titanate, tetraethyl titanate, titanium propanolate, titanium tetrachloride, titanyl sulfate, or any several mixture, the mol ratio in LiFePO4 and titanium source is 1:0.02～1.3.
3. preparation method according to claim 1, is characterized in that: described reducing agent is the one in potassium borohydride, sodium borohydride, or the mixture of the two, and the mol ratio in reducing agent and titanium source is 1:0.2～0.8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410354480.1A CN104124452B (en) | 2014-07-24 | 2014-07-24 | A kind of coated lithium iron phosphate positive material of titanium compound and preparation method thereof that conducts electricity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410354480.1A CN104124452B (en) | 2014-07-24 | 2014-07-24 | A kind of coated lithium iron phosphate positive material of titanium compound and preparation method thereof that conducts electricity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104124452A CN104124452A (en) | 2014-10-29 |
| CN104124452B true CN104124452B (en) | 2016-05-18 |
Family
ID=51769789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410354480.1A Active CN104124452B (en) | 2014-07-24 | 2014-07-24 | A kind of coated lithium iron phosphate positive material of titanium compound and preparation method thereof that conducts electricity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104124452B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104934572B (en) * | 2015-04-23 | 2017-10-03 | 金川集团股份有限公司 | A kind of preparation method of nickel cobalt aluminium lithium/titanium dioxide composite positive pole |
| CN104779370B (en) * | 2015-04-23 | 2017-03-15 | 天津巴莫科技股份有限公司 | A kind of method for improving lithium-ion-power cell cobalt nickel oxide aluminium lithium performance |
| CN105406041B (en) * | 2015-11-05 | 2017-09-01 | 盐城工学院 | A kind of hollow titanium composite material, preparation method and application |
| CN106064811B (en) * | 2016-05-31 | 2017-09-29 | 百川化工(如皋)有限公司 | A kind of preparation method of ferric phosphate |
| CN105932261A (en) * | 2016-06-30 | 2016-09-07 | 湖南桑顿新能源有限公司 | Lithium manganate cathode material and preparation method thereof |
| CN107799731A (en) * | 2016-09-01 | 2018-03-13 | 常州博杰新能源材料有限公司 | A kind of TiB2Coat nickel-cobalt lithium manganate cathode material and preparation method thereof |
| CN112239227B (en) * | 2020-10-29 | 2023-07-04 | 龙佰集团股份有限公司 | Preparation method of conductive titanium dioxide |
| CN112713272B (en) * | 2020-12-18 | 2022-11-18 | 浙江金鹰瓦力新能源科技有限公司 | Preparation method of modified lithium battery positive electrode material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005076391A1 (en) * | 2004-02-07 | 2005-08-18 | Lg Chem, Ltd. | Electrode additives coated with electro conductive material and lithium secondary comprising the same |
| CN101070148B (en) * | 2007-05-22 | 2010-05-19 | 无锡市凯天星电光材料有限公司 | Method for preparing lithium iron phosphate as lithium ion cell positive-pole material |
| CN101580238B (en) * | 2009-06-21 | 2011-04-20 | 海特电子集团有限公司 | Method for manufacturing composite lithium iron phosphate material and composite lithium iron phosphate material manufactured thereof |
-
2014
- 2014-07-24 CN CN201410354480.1A patent/CN104124452B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104124452A (en) | 2014-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104124452B (en) | A kind of coated lithium iron phosphate positive material of titanium compound and preparation method thereof that conducts electricity | |
| Wang et al. | Formation and modification of cathode electrolyte interphase: A mini review | |
| CN102044666B (en) | Method for preparing lithium iron phosphate composite material for lithium cells | |
| CN105895879B (en) | Fluorine-doped carbon-coated positive electrode composite material and preparation method and application thereof | |
| CN106450265B (en) | A kind of situ Nitrogen Doping carbon coating lithium titanate combination electrode material and preparation method thereof | |
| CN107275606B (en) | Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof | |
| CN104466135A (en) | Method for coating conductive polymer on Ni-Co-Mn acid lithium positive electrode material | |
| CN104638242A (en) | Method for synthesizing lithium ion battery cathode material lithium iron phosphate through in situ polymerizing and cladding | |
| CN105460917A (en) | Nitrogen-doped carbon nanotube adopting hierarchical structure and preparation method | |
| CN109686948B (en) | Preparation method of composite positive electrode material of lithium-sulfur battery | |
| CN102856553A (en) | Preparation method of hydrothermal synthesis carbon coated lithium iron phosphate | |
| CN106410153A (en) | Titanium nitride-cladded nickel titanate composite material as well as preparation method and application thereof | |
| CN106935838A (en) | The method for preparing the LiFePO4 quaternary composite of unidirectional preferential growth high electrochemical activity | |
| CN108963267A (en) | The preparation method of three-dimensional porous carbon coating zinc oxide collector for lithium an- ode | |
| CN105470468A (en) | Fluorine-doped lithium ferric manganese phosphate cathode material and preparation method thereof | |
| CN102945952A (en) | Method for preparing anode material carbon coated lithium titanate for lithium ion power batteries | |
| CN102157727B (en) | Preparation method for nano MnO of negative electrode material of lithium ion battery | |
| CN105514375A (en) | Carbon-coated Na0.55 Mn2O4.1.5H2O nanocomposite and preparation method thereof | |
| CN105236432A (en) | Preparation method of manganese lithium silicate cathode material | |
| CN105244500A (en) | Preparation method and application of b-axial LiFePO<4>/C nano flake material | |
| CN104577090A (en) | Method for preparing carbon and oxide composite modified lithium titanate material | |
| CN103107332B (en) | A kind of lithium iron phosphate positive material and preparation method thereof | |
| CN104332594A (en) | Silicon-based negative electrode material and preparation method and application thereof | |
| CN103474661A (en) | Preparation method of nanometer lithium iron phosphate anode material for lithium ion battery | |
| CN113991103A (en) | Aqueous lithium ion battery NaTi2(PO4)3Preparation method of/C negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |