CN108862230B - Treatment method of lithium iron phosphate superfine powder material - Google Patents

Treatment method of lithium iron phosphate superfine powder material Download PDF

Info

Publication number
CN108862230B
CN108862230B CN201811085446.3A CN201811085446A CN108862230B CN 108862230 B CN108862230 B CN 108862230B CN 201811085446 A CN201811085446 A CN 201811085446A CN 108862230 B CN108862230 B CN 108862230B
Authority
CN
China
Prior art keywords
iron phosphate
lithium iron
particles
sintering
powder material
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
Application number
CN201811085446.3A
Other languages
Chinese (zh)
Other versions
CN108862230A (en
Inventor
郅晓科
王芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Xianzhong New Energy Technology Co ltd
Original Assignee
Tianjin Xianzhong New Energy Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianjin Xianzhong New Energy Technology Co ltd filed Critical Tianjin Xianzhong New Energy Technology Co ltd
Priority to CN201811085446.3A priority Critical patent/CN108862230B/en
Publication of CN108862230A publication Critical patent/CN108862230A/en
Application granted granted Critical
Publication of CN108862230B publication Critical patent/CN108862230B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Abstract

The invention discloses a processing method of a lithium iron phosphate superfine powder material, which comprises the steps of putting lithium iron phosphate fine powder into a rotary mixer, spraying a carbon source binder solution in the rotating process, and forming particles after the powder and the binder are bonded in the rotating process of the mixer; drying the particles to remove moisture; thirdly, the dried particles are placed into a sintering furnace for sintering, and are calcined under the atmosphere condition of nitrogen and steam, so that the particles are sintered into large-particle lithium iron phosphate aggregates again, and the aggregates are crushed to obtain a lithium iron phosphate finished product meeting the particle size requirement. The invention adopts the carbon source which can be cracked to carry out re-granulation, the granulated lithium iron phosphate fine powder is sintered into coarse aggregates, the coarse aggregates can be manufactured into the lithium iron phosphate finished product which meets the process system particle size through the subsequent crushing process, and in order to prevent the carbon content from increasing, a small amount of water vapor is added in the sintering process to absorb carbon and convert the carbon into carbon monoxide to reduce the carbon content.

Description

Treatment method of lithium iron phosphate superfine powder material
Technical Field
The invention relates to the field of preparation of lithium ion battery anode materials, in particular to a treatment method of a lithium iron phosphate superfine powder material.
Background
Among the positive electrode materials for lithium ion batteries, lithium iron phosphate (LiFePO)4) The lithium ion battery has the advantages of no toxicity, low price, good safety, abundant resources and the like, is widely concerned, and is considered to be a preferred anode material of the lithium ion battery for electric vehicles and energy storage power stations.
The lithium ion battery is generally manufactured by the processes of mixing, sintering, airflow crushing, sieving and the like. In the jet milling process, in order to crush the lithium iron phosphate material, a supersonic air collision method is generally adopted to crush the particles. Then the product with proper grain size is prepared by classification and cyclone separation. The fine powder generated by the over-crushing is collected by a dust collector. Generally, the fine powder collected in the dust collector accounts for about 20% of the total amount, and reaches 30% as high. The fine powder has the general particle size of below 1um, large specific surface area, poor activity and high carbon content, and has poor processing performance when being used for processing a lithium ion battery. Many lithium iron phosphate plants have a large inventory of fine powders, which is difficult to utilize, resulting in a substantial increase in production costs.
The lithium iron phosphate fine powder is generally a carbon-coated lithium iron phosphate particle. If a common binder (such as styrene butadiene rubber, sodium carboxymethyl cellulose, polyvinylidene fluoride and the like) is added for granulation, an insulating layer is generated among particles, and the internal resistance of a battery system is increased. If the method of thermal cracking is carried out by adding sugar granulation, the carbon content can be obviously improved, and the specific surface area is increased.
With the rapid development of the lithium iron phosphate industry in China, the treatment of fine powder becomes urgent and becomes a problem to be solved urgently by manufacturers of lithium iron phosphate materials.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for treating a lithium iron phosphate superfine powder material with low carbon content and low fine powder content.
In order to solve the technical problems, the invention adopts the technical scheme that: a treatment method of a lithium iron phosphate superfine powder material comprises the following steps:
the method comprises the steps of putting lithium iron phosphate fine powder into a rotary mixer, spraying a carbon source binder solution in the rotating process, and forming particles after powder and the binder are bonded in the rotating process of the mixer;
drying the particles to remove moisture;
thirdly, the dried particles are placed into a sintering furnace for sintering, and are calcined under the atmosphere condition of nitrogen and steam, so that the particles are sintered into large-particle lithium iron phosphate aggregates again, and the aggregates are crushed to obtain a lithium iron phosphate finished product meeting the particle size requirement.
The carbon source binder is one of glucose, xylitol, polyethylene and polyvinyl butyral.
The solvent of the carbon source binder solution is water, ethanol or methanol.
The mass concentration of the carbon source binder solution is 1-20%.
The proportion of the carbon source binder in the mixed dry product is 0.5-10 percent, and the percentage is mass percent.
The drying temperature for drying the particles in the step (2) is 80-150 ℃.
The volume ratio of the nitrogen to the water vapor is 10 (0.1-10).
The sintering conditions in the step (3) are as follows: sintering at 800 ℃ for 0.5-12 hours at 500-.
The invention has the beneficial effects that: the invention adopts the carbon source which can be cracked to carry out re-granulation, the granulated lithium iron phosphate fine powder is sintered into coarse aggregates, the coarse aggregates can be manufactured into the lithium iron phosphate finished product which meets the process system particle size through the subsequent crushing process, and in order to prevent the carbon content from increasing, a small amount of water vapor is added in the sintering process to absorb carbon and convert the carbon into carbon monoxide to reduce the carbon content.
Detailed Description
The present invention is illustrated by the following embodiments, all operations and data are illustrative and not restrictive, and the scope of the present invention is not limited thereto.
The treatment method of the lithium iron phosphate superfine powder material comprises the following steps:
the method comprises the steps of putting lithium iron phosphate fine powder into a rotary mixer, spraying a carbon source binder solution in the rotating process, and forming particles after powder and the binder are bonded in the rotating process of the mixer;
drying the particles to remove moisture;
thirdly, the dried particles are placed into a sintering furnace for sintering, and are calcined under the atmosphere condition of nitrogen and steam, so that the particles are sintered into large-particle lithium iron phosphate aggregates again, and the aggregates are crushed to obtain a lithium iron phosphate finished product meeting the particle size requirement.
The carbon source binder is one of glucose, xylitol, polyethylene and polyvinyl butyral.
The solvent of the carbon source binder solution is water, ethanol or methanol.
The mass concentration of the carbon source binder solution is 1-20%.
The proportion of the carbon source binder in the mixed dry product is 0.5-10 percent, and the percentage is mass percent.
The drying temperature for drying the particles in the step (2) is 80-150 ℃.
The volume ratio of the nitrogen to the water vapor is 10 (0.1-10).
The sintering conditions in the step (3) are as follows: sintering at 800 ℃ for 0.5-12 hours at 500-.
The invention adopts a carbon source which can be cracked to carry out re-granulation. The granulated lithium iron phosphate fine powder is sintered into a coarse aggregate, and can be prepared into a lithium iron phosphate finished product with a particle size according with a process system through a subsequent crushing process. To prevent the increase of carbon content, we added a small amount of water vapor during the sintering process. Water vapor can consume carbon through the following pathway:
C+H2O→CO+H2
the carbon monoxide and hydrogen produced can be vented to the outside of the furnace. This allows the carbon content to be reduced by the introduction of water vapour. The proportion of the water vapor and the introduction time are controlled, so that the proportion of the carbon content in the product can be effectively controlled.
Example 1
First, 5g of anhydrous glucose is dissolved in 495g of distilled water to prepare a glucose aqueous solution with a mass fraction of 1%. Then D is50995Kg of fine lithium iron phosphate powder (carbon content: 2.5%) having an average particle size of 0.85um was placed in a rotary mixer, and the above aqueous glucose solution was sprayed during rotation for 10 minutes. The rotation was continued for 2 hours after pressing. At this time, the lithium iron phosphate fine powder is gradually adhered to form a wet ball due to the snowball effect.
Drying the wet balls in an oven at 80 ℃ for 2 hours to form dry balls. Wherein the mass proportion of the binder in the mixed dry balls is 0.5 percent.
Thirdly, continuously introducing mixed gas of nitrogen and steam in a volume ratio of 10:0.1 into the dry ball in an atmosphere sintering furnace, and heating and sintering. The sintering schedule was 500 ℃ for 12 hours.
After the sintered lithium iron phosphate material is subjected to jet milling, D50(average particle size) 1.8 μm, carbon content 2.2%. The electrochemical performance is unchanged.
Example 2
50Kg of xylitol is dissolved in 950Kg of distilled water to prepare a xylitol aqueous solution with the mass fraction of 5%. Then D is50950Kg of fine lithium iron phosphate powder (carbon content: 1.85%) having an average particle size of 0.6um was placed in a rotary millAnd (4) spraying the xylitol aqueous solution in the rotating process by using a mixer, wherein the spraying is finished within 60 minutes. The rotation was continued for 5 hours after the pressing. At this time, the fine lithium iron phosphate powder gradually adheres to form wet balls.
Drying the wet balls in an oven for 4 hours at 120 ℃ to form dry balls. Wherein the mass proportion of the binder in the mixed dry balls is 5 percent.
Thirdly, continuously introducing mixed gas of nitrogen and steam in a volume ratio of 10:2 into the dry ball in an atmosphere sintering furnace, and heating and sintering. The sintering system is 800 ℃ and 0.5 hour.
After the sintered lithium iron phosphate material is subjected to jet milling, D50(average particle size) 1.55 μm, carbon content 1.60%. The electrochemical performance is unchanged.
Example 3
Firstly, 100Kg of polyvinyl butyral is dissolved in 900Kg of absolute ethyl alcohol to prepare a polyvinyl butyral solution with the mass fraction of 10%. Then D is50900Kg of fine lithium iron phosphate powder (carbon content: 2.23%) having an average particle size of 0.4. mu.m was put in a rotary mixer, and the polyvinyl butyral solution was sprayed during the rotation for 30 minutes. The rotation was continued for 3 hours after the pressing. At this time, the fine lithium iron phosphate powder gradually adheres to form wet balls.
Drying the wet balls in an oven for 2 hours at 105 ℃ to form dry balls. Wherein the mass proportion of the binder in the mixed dry balls is 10 percent.
Thirdly, continuously introducing mixed gas of nitrogen and steam in a volume ratio of 10:1 into the dry ball in an atmosphere sintering furnace, and heating and sintering. The sintering system was 700 ℃ for 2 hours. After the sintered lithium iron phosphate material is subjected to jet milling, D50(average particle size) 1.7 μm and carbon content 2.1%. The electrochemical performance is unchanged.
The above-mentioned embodiments are only for illustrating the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and to carry out the same, and the present invention shall not be limited to the embodiments, i.e. the equivalent changes or modifications made within the spirit of the present invention shall fall within the scope of the present invention.

Claims (6)

1. A treatment method of a lithium iron phosphate superfine powder material is characterized by comprising the following steps:
the method comprises the steps of putting lithium iron phosphate fine powder into a rotary mixer, spraying a carbon source binder solution in the rotating process, and forming particles after powder and the binder are bonded in the rotating process of the mixer;
drying the particles to remove moisture;
thirdly, the dried particles are placed into a sintering furnace for sintering, and are calcined under the atmosphere condition of nitrogen and steam, so that the particles are sintered into large-particle lithium iron phosphate aggregates again, and the aggregates are crushed to obtain a lithium iron phosphate finished product meeting the particle size requirement; the volume ratio of the nitrogen to the water vapor is 10 (0.1-10), and the sintering conditions are as follows: sintering at 800 ℃ for 0.5-12 hours at 500-.
2. The method for processing the lithium iron phosphate superfine powder material as claimed in claim 1, wherein the carbon source binder is one of glucose, xylitol, polyethylene and polyvinyl butyral.
3. The method for processing the lithium iron phosphate ultrafine powder material according to claim 1, wherein a solvent of the carbon source binder solution is water, ethanol or methanol.
4. The method for processing the lithium iron phosphate superfine powder material as recited in claim 1, wherein the mass concentration of the carbon source binder solution is 1-20%.
5. The method for processing the lithium iron phosphate superfine powder material as claimed in claim 1, wherein the proportion of the carbon source binder in the mixed dried product is 0.5-10% by mass.
6. The method for processing the lithium iron phosphate ultrafine powder material according to claim 1, wherein the drying temperature for drying the particles in the step (2) is 80-150 ℃.
CN201811085446.3A 2018-09-18 2018-09-18 Treatment method of lithium iron phosphate superfine powder material Active CN108862230B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811085446.3A CN108862230B (en) 2018-09-18 2018-09-18 Treatment method of lithium iron phosphate superfine powder material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811085446.3A CN108862230B (en) 2018-09-18 2018-09-18 Treatment method of lithium iron phosphate superfine powder material

Publications (2)

Publication Number Publication Date
CN108862230A CN108862230A (en) 2018-11-23
CN108862230B true CN108862230B (en) 2021-10-08

Family

ID=64324368

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811085446.3A Active CN108862230B (en) 2018-09-18 2018-09-18 Treatment method of lithium iron phosphate superfine powder material

Country Status (1)

Country Link
CN (1) CN108862230B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112952097A (en) * 2021-02-23 2021-06-11 贵州安达科技能源股份有限公司 Lithium iron phosphate anode material and preparation method and application thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102303859A (en) * 2011-07-20 2012-01-04 彩虹集团公司 Preparation method of lithium iron phosphate material
CN102651475A (en) * 2012-05-28 2012-08-29 深圳市贝特瑞新能源材料股份有限公司 Synthesizing method of anode material lithium iron phosphate of lithium ion battery
CN102881903A (en) * 2012-10-23 2013-01-16 兰州理工大学 Preparation method of porous lithium iron phosphate powder
CN104409692A (en) * 2014-11-19 2015-03-11 上海纳米技术及应用国家工程研究中心有限公司 Modification method for electrode material for lithium ion battery
CN105576220A (en) * 2016-03-21 2016-05-11 河北工业大学 Preparation method of porous carbon-coated lithium iron phosphate anode material
CN105655548A (en) * 2014-12-03 2016-06-08 中国电子科技集团公司第十八研究所 Method for uniform carbon coating on lithium iron phosphate surface
CN106299251A (en) * 2015-05-25 2017-01-04 深圳市沃特玛电池有限公司 A kind of preparation method of electrokinetic cell composite positive pole
CN107204430A (en) * 2017-07-06 2017-09-26 新沂市中诺新材料科技有限公司 A kind of method that utilization wheat stalk prepares sodium ion battery electrode material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101294335B1 (en) * 2012-05-25 2013-08-16 한국과학기술연구원 Fabricating method of lifepo4 cathode electroactive material for lithium secondary battery by recycling, lifepo4 cathode electroactive material for lithium secondary battery, lifepo4 cathode and lithium secondary battery fabricated thereby

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102303859A (en) * 2011-07-20 2012-01-04 彩虹集团公司 Preparation method of lithium iron phosphate material
CN102651475A (en) * 2012-05-28 2012-08-29 深圳市贝特瑞新能源材料股份有限公司 Synthesizing method of anode material lithium iron phosphate of lithium ion battery
CN102881903A (en) * 2012-10-23 2013-01-16 兰州理工大学 Preparation method of porous lithium iron phosphate powder
CN104409692A (en) * 2014-11-19 2015-03-11 上海纳米技术及应用国家工程研究中心有限公司 Modification method for electrode material for lithium ion battery
CN105655548A (en) * 2014-12-03 2016-06-08 中国电子科技集团公司第十八研究所 Method for uniform carbon coating on lithium iron phosphate surface
CN106299251A (en) * 2015-05-25 2017-01-04 深圳市沃特玛电池有限公司 A kind of preparation method of electrokinetic cell composite positive pole
CN105576220A (en) * 2016-03-21 2016-05-11 河北工业大学 Preparation method of porous carbon-coated lithium iron phosphate anode material
CN107204430A (en) * 2017-07-06 2017-09-26 新沂市中诺新材料科技有限公司 A kind of method that utilization wheat stalk prepares sodium ion battery electrode material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Nanocomposite of LiFePO4 and Mesoporous Carbon for High Power Cathode of Lithium Rechargeable Batteries";Jun-Il Kim et al;《Journal of Nanoscience and Nanotechnology》;20121101;第12卷;第8475-8480页 *
"碳-水蒸气气化反应新机理探讨";盖希坤等;《化学世界》;20150825(第8期);第492页 *

Also Published As

Publication number Publication date
CN108862230A (en) 2018-11-23

Similar Documents

Publication Publication Date Title
CN104300119B (en) A kind of preparation method of lithium iron phosphate positive material
CN100356617C (en) Nanometer phosphate ferrolithium/carbon composite materials, production of solid-phase and use thereof
CN101734637B (en) Preparation method of anode material vanadium-lithium phosphate powder for lithium ion battery
CN108706564A (en) A kind of preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate
CN101394015A (en) Regeneration method for waste lithium ion phosphate positive pole material
CN109167028B (en) Regeneration preparation method of lithium iron phosphate/carbon composite material
CN103427069A (en) Lithium ion battery composite anode material and preparation thereof
CN111422852B (en) Preparation method of iron vanadium phosphate
CN106356515A (en) Preparation method of silicon oxide composite material
CN105449201B (en) A kind of preparation method of power-type high vibration high density lithium iron phosphate composite material
CN102623701B (en) Preparation method for low-temperature nanometer lithium iron phosphate cathode material
CN115432698B (en) Carbon secondary particle and preparation method thereof, artificial graphite and preparation method thereof, lithium ion battery anode material and lithium ion battery
CN107792891B (en) Preparation method of nickel cobalt lithium manganate powder
CN108862230B (en) Treatment method of lithium iron phosphate superfine powder material
CN103474653A (en) Preparation method for lithium iron phosphate
CN114759178A (en) High-compaction lithium iron phosphate positive electrode material, preparation method thereof, positive electrode and battery
CN102945951A (en) Preparation of lead carbon composite material and method manufacturing lead carbon batteries by utilizing material
CN106450186A (en) Preparation method for lithium manganese silicate/carbon composite material used as positive electrode material of lithium ion battery, and positive electrode slurry and application
CN113540461A (en) Preparation method of lithium iron phosphate coated by full carbon layer
CN112310374A (en) Method for preparing high-compaction low-specific-surface-area lithium iron phosphate by sectional grinding-spray drying
CN108682853B (en) Preparation method of lithium iron phosphate and lithium iron phosphate cathode material prepared by same
KR101564373B1 (en) Method of preparing artificial graphite negative electrode material for rechargeable lithium battery
CN102205954A (en) Method for synthesizing high-density lithium iron phosphate material
CN111313011B (en) Preparation method of low-cost high-performance lithium iron phosphate
CN114141993A (en) Processing technology of composite modified graphite negative electrode with good cycling stability

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A treatment method of lithium iron phosphate ultrafine powder material

Effective date of registration: 20220329

Granted publication date: 20211008

Pledgee: Tianjin Kerong Financing Guarantee Co.,Ltd.

Pledgor: TIANJIN XIANZHONG NEW ENERGY TECHNOLOGY CO.,LTD.

Registration number: Y2022120000012

PE01 Entry into force of the registration of the contract for pledge of patent right
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20230410

Granted publication date: 20211008

Pledgee: Tianjin Kerong Financing Guarantee Co.,Ltd.

Pledgor: TIANJIN XIANZHONG NEW ENERGY TECHNOLOGY CO.,LTD.

Registration number: Y2022120000012

PC01 Cancellation of the registration of the contract for pledge of patent right