CN108878822B - Preparation method of coated nano iron phosphate composite material - Google Patents

Preparation method of coated nano iron phosphate composite material Download PDF

Info

Publication number
CN108878822B
CN108878822B CN201810648118.3A CN201810648118A CN108878822B CN 108878822 B CN108878822 B CN 108878822B CN 201810648118 A CN201810648118 A CN 201810648118A CN 108878822 B CN108878822 B CN 108878822B
Authority
CN
China
Prior art keywords
iron phosphate
composite material
preparing
gas
solution
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
CN201810648118.3A
Other languages
Chinese (zh)
Other versions
CN108878822A (en
Inventor
郑夏莲
马元好
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.)
Yichun University
Original Assignee
Yichun University
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 Yichun University filed Critical Yichun University
Priority to CN201810648118.3A priority Critical patent/CN108878822B/en
Publication of CN108878822A publication Critical patent/CN108878822A/en
Application granted granted Critical
Publication of CN108878822B publication Critical patent/CN108878822B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/36—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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Cosmetics (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses a preparation method of a nano iron phosphate coated composite material, which comprises the steps of 1) 1, taking Fe according to molar ratio2+Preparing a ferric phosphate mixed solution from the compound, an oxidant and phosphoric acid; taking alkali solution according to a molar ratio; 2) the mixed solution and high-pressure gas are collided at high speed and are pressurized and blended, so that the gas is fully coated around the iron phosphate to form a nano iron phosphate gas capsule; the iron phosphate prepared by the method has the advantages of high purity, high tap density, stability and easiness in purification, and is suitable for large-scale manufacturing.

Description

Preparation method of coated nano iron phosphate composite material
The technical field is as follows:
the invention relates to a preparation method of iron phosphate; in particular to a preparation method of a coated nano iron phosphate composite material.
Background art:
with the development of science and technology, new energy vehicles are widely used as important vehicles, and power batteries used by the new energy vehicles are generally lithium ion batteries, for example, lithium ion batteries using lithium iron phosphate as a raw material are one of the power batteries of the new energy vehicles. The lithium iron phosphate has strong structural stability and can not release oxygen at high temperature, so that the safety problem caused by the lithium battery anode material is avoided. Therefore, the iron phosphate material for preparing the lithium iron phosphate is widely applied.
In recent years, a hot spot is formed when an iron phosphate material is used as a synthetic material of a positive electrode material of a lithium ion battery, but the iron phosphate itself can also be used as an insert material of the lithium ion battery material, and after the iron phosphate is used as the synthetic material, the iron phosphate itself is likely to adhere moisture to form crystal water and is not easy to dry, or the iron phosphate itself adheres to other materials, so that impurities are generated, how to form protection during the material synthesis, and the coated nano iron phosphate composite material forming the air-bag material is an important direction for the current battery material research.
In the existing preparation of the iron phosphate composite material, the prepared material has low purity, and the prepared coated nano iron phosphate composite material is not easy to dry. On the other hand, the prior preparation method has the defects that a large amount of water resources are needed, and on the other hand, the subsequent treatment process is difficult and the environmental treatment pressure is high due to the use of a large amount of sulfate ions.
The invention content is as follows:
the invention aims to provide a preparation method of a coated nano iron phosphate composite material, which is Fe2+Compound, oxidant, phosphoric acid or Fe3+ The compound and phosphoric acid are used as raw materials, and the prepared nano iron phosphate composite material is characterized in that a gas coating layer is formed around iron phosphate; has the advantages of stability and easy purification, and is suitable for large-scale preparation; the production cost is low.
The invention discloses a preparation method of a coated nano iron phosphate composite material, which comprises the following steps:
1) preparing raw materials, namely preparing Fe according to a molar mass ratio2+Compound, oxidant, phosphoric acid or Fe3+ Stirring, mixing and reacting the compound and phosphoric acid to prepare an iron phosphate mixed solution; and preparing alkali into alkali liquor;
2) preparing a nano gas bag solution, namely performing high-speed collision and pressurized blending reaction on the iron phosphate mixed solution prepared in the step 1) and gas in a high-pressure gas reaction device to promote the gas to be fully coated around the iron phosphate mixed solution to form the nano gas bag solution;
3) and (3) placing the nano air-bag solution prepared in the step 2) and the alkali liquor prepared in the step 1) in a reaction kettle for high-speed stirring or air-jet reaction to form gas-liquid blended coated nano coating emulsion, namely the coated nano iron phosphate composite material.
Preferably, it is said Fe2+The compound is ferrous chloride or ferrous acetate or ferrous sulfate ferrous salt; the oxidant is hydrogen peroxide or ozone; said Fe3+The compound is ferric iron salt such as ferric nitrate or ferric chloride.
Preferably, the alkali liquor is any one of potassium hydroxide solution, sodium hydroxide solution and ammonia water.
Further, the method controls the iron: the mass mol ratio of the phosphorus is 1.05-1.2: 1.
Preferably, the gas is any one of nitrogen, argon, helium and neon.
Further, the molar mass ratio of Fe2+Compound and oxidizing agentAnd stirring and mixing the phosphoric acid to prepare the iron phosphate mixed solution, wherein the stirring and mixing reaction temperature is controlled to be 55-65 ℃, and the reaction time is 40-90 minutes.
The preparation method of the coated nano iron phosphate composite material disclosed by the invention has the beneficial effects that: firstly, the invention introduces gas materials to form a gas condensation state through the integral formula design, and the prepared nano iron phosphate composite material has high purity and is easy to dry. The preparation of the nano iron phosphate composite material in the prior art needs a large amount of water resources, so that the water consumption is small; on the other hand, because sulfate ions are not used, the subsequent treatment process is simple, and the pressure on environmental treatment is small. The resulting gas coating was formed around the iron phosphate. Has the advantages of stability and easy purification, and is suitable for large-scale production.
The specific implementation mode is as follows: the present invention will be described in further detail with reference to specific examples.
The technical scheme adopted by the invention comprises the following steps:
a process for preparing the nano-class iron phosphate coated composite material includes such steps as preparing Fe2+The preparation process of the compound, the oxidant and the phosphoric acid as raw materials mainly comprises the following preparation steps: the mass mole portion of the components is,
1) taking 1.1 parts of ferrous chloride and 1.5 parts of hydrogen peroxide, stirring and reacting for 1 hour at the temperature of 60 ℃, slowly dripping 1 part of phosphoric acid, stirring at high speed to form turbid solution, namely iron phosphate mixed solution,
2) adding the mixed solution of the ferric phosphate obtained in the step 1) into a high-pressure gas reaction device, namely a high-pressure gas reaction kettle, colliding with high-pressure nitrogen under a pressurized state to react so that the gas is fully coated around the mixed solution of the ferric phosphate to form a nano gas-bag solution or a layer of gas-bag solution,
3) preparing two parts of ammonia water into an ammonia water solution with the mass concentration of 10%, and then colliding the ammonia water solution with the glue solution in the step 2), namely a layer of air-bag solution, through a spray gun port by adopting an air injection reaction so that the ammonia water solution is coated around the air bag, namely the nano air-bag solution, to form a three-layer solution; namely the coated nano iron phosphate composite material.
Said Fe2+The compound is one or more of ferrous chloride, ferrous acetate and ferrous sulfate. The oxidant is one of hydrogen peroxide and ozone. Said Fe3+ Is any one of ferric nitrate, ferric chloride or ferric sulfate.
The alkali liquor is one of potassium hydroxide, sodium hydroxide or ammonia water. The gas is any one of nitrogen, argon, helium and neon.
Example 1:
the preparation method of the coated nano iron phosphate composite material of the embodiment comprises the following components in formula 1:
table 1: preparation method of coated nano iron phosphate composite material
Raw materials Molar fraction
Ferric chloride 1.05
Phosphoric acid 1
Nitrogen gas 5
Aqueous ammonia 2
Example 2, the same method for preparing a coated nano ferric phosphate composite material as in example 1 except for the following description, has the following formulation:
table 2: preparation method of coated nano iron phosphate composite material
Raw materials Molar fraction
Ferrous chloride or oxalate 1.1
Phosphoric acid 1
Ozone generator 1.5
Potassium hydroxide 2
Nitrogen gas 5
According to the invention, through the design of an integral formula, a gas material is introduced to form a gas condensation state, and the prepared coated nano iron phosphate composite material has high purity and is easy to dry.

Claims (5)

1. A preparation method of a coated nano iron phosphate composite material comprises the following steps:
step 1) preparing raw materials, namely preparing Fe according to a molar mass ratio2+Compound, oxidant, phosphoric acid or Fe3+ Compound (I)Stirring and mixing the mixed solution and phosphoric acid to react to prepare a ferric phosphate mixed solution; preparing alkali into alkali liquor;
step 2) preparing a nano gas bag solution, namely performing high-speed collision and pressurization blending reaction on the iron phosphate mixed solution prepared in the step 1) and gas in a high-pressure gas reaction device to promote the gas to be fully coated around the iron phosphate mixed solution to form the nano gas bag solution;
step 3) placing the nano air-bag solution and the alkali liquor prepared in the step 2) in a reaction kettle for high-speed stirring or air-jet reaction to form air-liquid blended coated nano coating emulsion, namely a coated nano iron phosphate composite material;
the gas is any one of nitrogen, argon, helium and neon.
2. The method for preparing coated nano iron phosphate composite material according to claim 1, characterized in that the Fe is2+The compound is ferrous chloride or ferrous acetate; the oxidant is hydrogen peroxide or ozone; said Fe3+The compound is ferric nitrate or ferric chloride.
3. The method for preparing the coated nano iron phosphate composite material according to claim 1, wherein the alkali solution is any one of potassium hydroxide solution, sodium hydroxide solution and ammonia water.
4. The method for preparing the coated nano iron phosphate composite material according to claim 1, wherein the ratio of iron: the mass mol ratio of the phosphorus is 1.05-1.15: 1.
5. The method for preparing coated nano iron phosphate composite material according to claim 1, wherein the molar mass ratio of Fe is adjusted to2+The iron phosphate mixed solution is prepared by stirring and mixing the compound, the oxidant and the phosphoric acid, wherein the stirring and mixing reaction temperature is controlled to be 55-65 ℃, and the reaction time is 40-90 minutes.
CN201810648118.3A 2018-06-22 2018-06-22 Preparation method of coated nano iron phosphate composite material Active CN108878822B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810648118.3A CN108878822B (en) 2018-06-22 2018-06-22 Preparation method of coated nano iron phosphate composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810648118.3A CN108878822B (en) 2018-06-22 2018-06-22 Preparation method of coated nano iron phosphate composite material

Publications (2)

Publication Number Publication Date
CN108878822A CN108878822A (en) 2018-11-23
CN108878822B true CN108878822B (en) 2021-04-09

Family

ID=64340423

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810648118.3A Active CN108878822B (en) 2018-06-22 2018-06-22 Preparation method of coated nano iron phosphate composite material

Country Status (1)

Country Link
CN (1) CN108878822B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009217946A (en) * 2008-03-07 2009-09-24 Hitachi Vehicle Energy Ltd Organic electrolytic solution secondary battery
JP2010108928A (en) * 2008-10-01 2010-05-13 Daiken Chemical Co Ltd Process of producing lithium cell active material, lithium cell active material, and lithium system secondary battery
CN101924204A (en) * 2010-01-21 2010-12-22 浙江大学 Method for preparing conducting film LiFePO4 cladding material containing nitrogen
CN104868118A (en) * 2015-04-07 2015-08-26 上海电力学院 Preparation method of sodium ion battery anode FePO4/Graphene composite
KR20160014461A (en) * 2014-07-29 2016-02-11 주식회사 엘지화학 Method for preparing positive-electrode comprising a step of drying by adding organic acid and positive-electrode prepared thereby
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
CN105800578A (en) * 2016-03-02 2016-07-27 杨第伦 Method for producing ultra-micro and nano iron phosphate by virtue of gas bubble liquid membrane process
CN106848247A (en) * 2017-03-01 2017-06-13 桂林理工大学 Method based on ferric phosphate Hydrothermal Synthesiss high-performance iron phosphate lithium/three-dimensional porous graphene composite material
CN107473196A (en) * 2017-09-30 2017-12-15 贵州微化科技有限公司 A kind of method of continuous production LITHIUM BATTERY high compacted density nano ferric phosphate

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1702373B1 (en) * 2003-12-23 2017-10-11 Universite De Montreal Process for preparing electroactive insertion compounds and electrode materials obtained therefrom

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009217946A (en) * 2008-03-07 2009-09-24 Hitachi Vehicle Energy Ltd Organic electrolytic solution secondary battery
JP2010108928A (en) * 2008-10-01 2010-05-13 Daiken Chemical Co Ltd Process of producing lithium cell active material, lithium cell active material, and lithium system secondary battery
CN101924204A (en) * 2010-01-21 2010-12-22 浙江大学 Method for preparing conducting film LiFePO4 cladding material containing nitrogen
KR20160014461A (en) * 2014-07-29 2016-02-11 주식회사 엘지화학 Method for preparing positive-electrode comprising a step of drying by adding organic acid and positive-electrode prepared thereby
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
CN104868118A (en) * 2015-04-07 2015-08-26 上海电力学院 Preparation method of sodium ion battery anode FePO4/Graphene composite
CN105800578A (en) * 2016-03-02 2016-07-27 杨第伦 Method for producing ultra-micro and nano iron phosphate by virtue of gas bubble liquid membrane process
CN106848247A (en) * 2017-03-01 2017-06-13 桂林理工大学 Method based on ferric phosphate Hydrothermal Synthesiss high-performance iron phosphate lithium/three-dimensional porous graphene composite material
CN107473196A (en) * 2017-09-30 2017-12-15 贵州微化科技有限公司 A kind of method of continuous production LITHIUM BATTERY high compacted density nano ferric phosphate

Also Published As

Publication number Publication date
CN108878822A (en) 2018-11-23

Similar Documents

Publication Publication Date Title
CN107093732B (en) A kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation method for anode material of lithium battery
CN102515129A (en) Preparation method for submicron battery-grade ferric phosphate
CN102887532B (en) Process for preparing potassium fluoride and co-producing white carbon black from fluosilicic acid
CN104538629A (en) Method for preparing spherical nano iron phosphate
CN107863530A (en) A kind of method that high-density lithium iron phosphate is prepared using siderite
CN101728560B (en) Method for preparing vanadium redox battery negative pole electrolyte
CN108878822B (en) Preparation method of coated nano iron phosphate composite material
CN109928375B (en) Method for preparing iron phosphate by using monocalcium phosphate
CN104263014A (en) Preparing method of high-purity active calcium carbonate used for coating
CN106654239B (en) A kind of interior carbon dope lithium ion battery material and preparation method thereof
CN102653921A (en) Alkali-resisting penetrating agent for cotton fabric mercerization
CN102392311A (en) Method for synthesizing lithium iron phosphate material by adopting electrostatic spinning
CN100565988C (en) A kind of preparation method for sulfur oxygen solid-oxide fuel battery anode
CN109802125A (en) A kind of anode material for compound lithium ion battery and preparation method thereof and a kind of lithium ion battery
CN106684435B (en) A kind of NaFePO4The preparation method of/C nano piece
CN111029571B (en) Preparation method of silicon dioxide uniformly doped iron phosphate
CN104362339B (en) Pure phase Li2FeSiO4 and preparation method of Li2FeSiO4 carbon-coated modified product
KR102122156B1 (en) Method of preparing lithium hydroxide
CN102623699B (en) Method for synthesizing high-performance lithium iron phosphate
CN111704122A (en) Preparation method of lithium iron phosphate cathode material of lithium ion battery
CN101226999A (en) Method for preparation of sulphur-oxygen solid-oxide fuel battery anode basal membrane
CN101901915B (en) Preparation of sulfur-oxygen solid oxide fuel cell anode
CN105742631A (en) Differential reaction crystallization industrial preparation method for high-purity nano-scale lithium iron phosphate
CN109148792A (en) A kind of method of modifying of water system lithium-air battery Ca-Ti ore type diaphragm
CN102381694A (en) Lithium ion battery electrode material synthesized by using full-solution process

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