CN103647080A - Preparation method of metal ion-LiFePo4-C composite material - Google Patents

Preparation method of metal ion-LiFePo4-C composite material Download PDF

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Publication number
CN103647080A
CN103647080A CN201310568704.4A CN201310568704A CN103647080A CN 103647080 A CN103647080 A CN 103647080A CN 201310568704 A CN201310568704 A CN 201310568704A CN 103647080 A CN103647080 A CN 103647080A
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China
Prior art keywords
mixture
lifepo4
composite material
metal ion
preparation
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CN201310568704.4A
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Chinese (zh)
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王维利
范未峰
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CHENGDU XINGNENG NEW MATERIALS CO LTD
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CHENGDU XINGNENG NEW MATERIALS CO LTD
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    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • H01M4/626—Metals
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a preparation method of a metal ion-LiFePo4-C composite material, which belongs to the technical field of energy material preparation. According to the invention, ascorbic acid is taken as an optimum carbon source, a coprecipitation method is used for preparing a LiFePO4/C composite cathode material, and then a ball milling method is used for preparing the metal ion-LiFePo4-C composite material by using magnesium and aluminum to partially substitute the lithium bite, so that specific energy and cycle stability of the composite material can be greatly increased, and the conductive capability is improved.

Description

The preparation method of metal ion-LiFePO4-C composite material
Technical field
The invention belongs to energy and material preparation technology field, relate to the preparation method of one metal ion species-LiFePO4-C composite material.
Background technology
Lithium rechargeable battery has that voltage is high, energy density is large, good cycle, etc. advantage, from last century, the nineties sony is widely used after releasing first lithium rechargeable battery, the research and development of lithium rechargeable battery are also subject to extensive concern.
In various storage lithium anode materials, LiFePO 4because security performance is good, have extended cycle life, the advantage such as raw material wide material sources, acyclic pollution shows one's talent, and from John professor B.Goodenough in 1997, finds first after the characteristic of its reversible doff lithium ion, battery circle has caused a great sensation.It is the focus of anode material for lithium-ion batteries research and development always.Particularly in recent years, along with various, improve going deep into of its high rate performance research, the chemical property of such material has reached realistic scale, and has realized part commercialization.Because of its feature with high energy density, cheap price, excellent fail safe, thought in the industry and most possibly become EV positive electrode for battery material.When it has prominent advantages, as EV positive electrode for battery material, also there is its fatal shortcoming: electrons/ions transfer rate is low to be unfavorable for high-powerly discharging and recharging, cryogenic property is poor.
Therefore, how to improve LiFePO 4high rate performance and bulk density, improve its conductive capability, these problems need to solve.
Summary of the invention
For addressing the above problem, the invention provides the preparation method of one metal ion species-LiFePO4-C composite material, can greatly improve specific energy and the cyclical stability of composite material, improve its conductive capability.
The present invention adopts following technical scheme:
The preparation method of one metal ion species-LiFePO4-C composite material, is characterized in that comprising the following steps:
(1) according to the ratio of mol ratio 1:1:1, take respectively LiOH-H20, reduction Fe powder and H3P04;
(2) three kinds of materials that take in step (1) are added and in deionized water, be made into mixed solution, and stirring reaction, to pH=3 ~ 3.5, obtains mixture A in blanket of nitrogen;
(3) in the mixture A in step (2), add ascorbic acid, obtain mixture B, 1 ~ 2 times of the amount that the addition of described ascorbic acid is reduction Fe amylaceous substance;
(4) the mixture B described in step (3) is dried, obtains mixture C;
(5) mixture C in step (4) and magnesium oxide, aluminium oxide are mixed in proportion, in the medium of absolute ethyl alcohol, high speed ball milling 5 ~ 8h, obtains mixture D;
(6) by mixture D 105-120 ℃ of oven dry, obtain mixture E;
(7) by mixture E in blanket of nitrogen, in the high-temperature calcination 4 ~ 6h of 500-750 ℃, obtain described metal ion-LiFePO4-C composite material.
Preferably, the temperature of the stirring reaction described in step (2) is 70 ℃.
Preferably, being dried as adopting high-speed centrifugal spray dryer to spray described in step (4) is dried.
Preferably, described spray-dired inlet temperature is that 220 ℃, feeding flow velocity are 15 mL/min.
Preferably, the rotating speed of the high speed ball milling described in step (5) is 180 ~ 240r/min.
Beneficial effect of the present invention is as follows:
1. the present invention first adopts coprecipitation to prepare LiFeP0 4/ C composite material, the ascorbic acid of selection is best carbon source, not only can avoid precursor synthetic in the oxidation of Fe (ll) component, carbonized product is Fe (lll) dephasign in reducible precursor also, thereby has improved LiFeP0 4purity and conductivity.
2. preparation method provided by the invention, is coated in process at carbon, and under hot environment, carbonized product makes Fe (IH) dephasign in precursor be reduced to Fe (ll), has improved mixing degree and the character of LiFeP04.The carbon source of reproducibility can be avoided the oxidation of Fe (ll) component in coprecipitation reaction.
3. preparation method provided by the invention, with magnesium and aluminum portions, substitute lithium position, the crystal structure of positive electrode is changed, improved Li+ and embedded an interface environments of moving out, improved electron conduction and the ionic conductivity in electrode material, made chemical property produce difference.
4. use preparation method provided by the invention, the metal ion-LiFePO4-C composite material being prepared from, can greatly improve specific energy and the cyclical stability of composite material, improves its conductive capability.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
embodiment 1
The preparation method of one metal ion species-LiFePO4-C composite material, comprises the following steps:
(1) according to the ratio of mol ratio 1:1:1, take respectively LiOH-H 20, reduction Fe powder and H 3p0 4;
(2) three kinds of materials that take are added and in deionized water, be made into mixed solution, and stirring reaction, to pH=3, obtains mixture A in blanket of nitrogen, the temperature of stirring reaction is 70 ℃;
(3) in mixture A, add ascorbic acid, obtain mixture B, 1 times of the amount that the addition of described ascorbic acid is reduction Fe amylaceous substance;
(4) mixture B is used high-speed centrifugal spray dryer spray dry, obtain mixture C;
(5) mixture C and magnesium oxide, aluminium oxide are mixed in proportion, in the medium of absolute ethyl alcohol, the rotating speed of high speed ball milling 5h(high speed ball milling is 240r/min), obtain mixture D;
(6) by mixture D 105-120 ℃ of oven dry, obtain mixture E;
(7) by mixture E in blanket of nitrogen, in the high-temperature calcination 4 ~ 6h of 500-750 ℃, obtain described metal ion-LiFePO4-C composite material.
embodiment 2
The preparation method of one metal ion species-LiFePO4-C composite material, is characterized in that comprising the following steps:
(1) according to the ratio of mol ratio 1:1:1, take respectively LiOH-H 20, reduction Fe powder and H 3p0 4;
(2) three kinds of materials that take are added and in deionized water, be made into mixed solution, and stirring reaction, to pH=3.5, obtains mixture A in blanket of nitrogen, the temperature of stirring reaction is 70 ℃;
(3) in mixture A, add ascorbic acid, obtain mixture B, 2 times of the amount that the addition of described ascorbic acid is reduction Fe amylaceous substance;
(4) mixture B is used high-speed centrifugal spray dryer spray dry (spray-dired inlet temperature is that 220 ℃, feeding flow velocity are 15 mL/min), and collect mixture C with cyclone separator;
(5) mixture C and magnesium oxide, aluminium oxide are mixed in proportion, in the medium of absolute ethyl alcohol, the rotating speed of high speed ball milling 7h(high speed ball milling is 200r/min), obtain mixture D;
(6) by mixture D 105-120 ℃ of oven dry, obtain mixture E;
(7) by mixture E in blanket of nitrogen, in the high-temperature calcination 4 ~ 6h of 500-750 ℃, obtain described metal ion-LiFePO4-C composite material.
embodiment 3
The preparation method of one metal ion species-LiFePO4-C composite material, is characterized in that comprising the following steps:
(1) according to the ratio of mol ratio 1:1:1, take respectively LiOH-H 20, reduction Fe powder and H 3p0 4;
(2) three kinds of materials that take are added and in deionized water, be made into mixed solution, and stirring reaction, to pH=3.2, obtains mixture A in blanket of nitrogen, the temperature of stirring reaction is 70 ℃;
(3) in mixture A, add ascorbic acid, obtain mixture B, 1.5 times of the amount that the addition of described ascorbic acid is reduction Fe amylaceous substance;
(4) mixture B is used high-speed centrifugal spray dryer spray dry (spray-dired inlet temperature is that 220 ℃, feeding flow velocity are 15 mL/min), and collect with cyclone separator, obtain mixture C;
(5) mixture C in step (4) and magnesium oxide, aluminium oxide are mixed in proportion, in the medium of absolute ethyl alcohol, the rotating speed of high speed ball milling 8h(high speed ball milling is 180r/min), obtain mixture D;
(6) by mixture D 105-120 ℃ of oven dry, obtain mixture E;
(7) by mixture E in blanket of nitrogen, in the high-temperature calcination 4 ~ 6h of 500-750 ℃, obtain described metal ion-LiFePO4-C composite material.

Claims (5)

1. the preparation method of one metal ion species-LiFePO4-C composite material, is characterized in that comprising the following steps:
(1) according to the ratio of mol ratio 1:1:1, take respectively LiOH-H 20, reduction Fe powder and H 3p0 4;
(2) three kinds of materials that take in step (1) are added and in deionized water, be made into mixed solution, and stirring reaction, to pH=3 ~ 3.5, obtains mixture A in blanket of nitrogen;
(3) in the mixture A in step (2), add ascorbic acid, obtain mixture B, 1 ~ 2 times of the amount that the addition of described ascorbic acid is reduction Fe amylaceous substance;
(4) the mixture B described in step (3) is dried, obtains mixture C;
(5) mixture C in step (4) and magnesium oxide, aluminium oxide are mixed in proportion, in the medium of absolute ethyl alcohol, high speed ball milling 5 ~ 8h, obtains mixture D;
(6) by mixture D 105-120 ℃ of oven dry, obtain mixture E;
(7) by mixture E in blanket of nitrogen, in the high-temperature calcination 4 ~ 6h of 500-750 ℃, obtain described metal ion-LiFePO4-C composite material.
2. the preparation method of metal ion-LiFePO4-C composite material according to claim 1, is characterized in that, the temperature of the stirring reaction described in step (2) is 70 ℃.
3. the preparation method of metal ion-LiFePO4-C composite material according to claim 1, is characterized in that, being dried as adopting high-speed centrifugal spray dryer to spray described in step (4) is dry.
4. the preparation method of metal ion-LiFePO4-C composite material according to claim 3, is characterized in that, described spray-dired inlet temperature is that 220 ℃, feeding flow velocity are 15 mL/min.
5. the preparation method of metal ion-LiFePO4-C composite material according to claim 1, is characterized in that, the rotating speed of the high speed ball milling that step (5) is described is 180 ~ 240r/min.
CN201310568704.4A 2013-11-15 2013-11-15 Preparation method of metal ion-LiFePo4-C composite material Pending CN103647080A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007092102A2 (en) * 2006-02-02 2007-08-16 Uchicago Argonne, Llc Lithium-ion batteries with intrinsic pulse overcharge protection
CN101442117A (en) * 2008-12-22 2009-05-27 上海电力学院 Method for preparing carbon-coating ferric phosphate lithium
CN102066241A (en) * 2008-04-17 2011-05-18 巴斯夫欧洲公司 Process for the preparation of crystalline lithium-, iron- and phosphate-comprising materials
CN102306753A (en) * 2011-09-03 2012-01-04 深圳市贝特瑞新能源材料股份有限公司 Full solid phase preparation method of lithium ion positive electrode material lithium iron phosphate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007092102A2 (en) * 2006-02-02 2007-08-16 Uchicago Argonne, Llc Lithium-ion batteries with intrinsic pulse overcharge protection
CN102066241A (en) * 2008-04-17 2011-05-18 巴斯夫欧洲公司 Process for the preparation of crystalline lithium-, iron- and phosphate-comprising materials
CN101442117A (en) * 2008-12-22 2009-05-27 上海电力学院 Method for preparing carbon-coating ferric phosphate lithium
CN102306753A (en) * 2011-09-03 2012-01-04 深圳市贝特瑞新能源材料股份有限公司 Full solid phase preparation method of lithium ion positive electrode material lithium iron phosphate

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Application publication date: 20140319