CN102303857A - Preparation method of nano iron phosphate with globulomer structure for lithium iron phosphate - Google Patents

Preparation method of nano iron phosphate with globulomer structure for lithium iron phosphate Download PDF

Info

Publication number
CN102303857A
CN102303857A CN201110201227A CN201110201227A CN102303857A CN 102303857 A CN102303857 A CN 102303857A CN 201110201227 A CN201110201227 A CN 201110201227A CN 201110201227 A CN201110201227 A CN 201110201227A CN 102303857 A CN102303857 A CN 102303857A
Authority
CN
China
Prior art keywords
iron phosphate
particle diameter
lithium iron
ball aggressiveness
preparation
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.)
Pending
Application number
CN201110201227A
Other languages
Chinese (zh)
Inventor
赵金鑫
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.)
Irico Group Corp
Original Assignee
Irico Group Corp
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 Irico Group Corp filed Critical Irico Group Corp
Priority to CN201110201227A priority Critical patent/CN102303857A/en
Publication of CN102303857A publication Critical patent/CN102303857A/en
Pending legal-status Critical Current

Links

Classifications

    • 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

  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a preparation method of nano iron phosphate (FePO4.2H2O) with a globulomer structure for lithium iron phosphate. The preparation method comprises the following steps: dissolving soluble compounds which respectively contain Fe<3+> and PO4<3-> to form a homogeneous phase solution, regulating pH value with an alkaline solution, carrying out water bath heating on a mixed liquid until the effective component of the mixed liquid is sufficiently precipitated to form a white flocculent suspension, filtering and washing; and preparing primary particles by using a liquid phase control crystallization process, and carrying out secondary pelleting with a spray drying process so as to obtain FePO4.2H2O having the globulomer structure and a particle diameter of 5-20 mu m, wherein FePO4.2H2O is formed by agglomeration of primary particles with a particle diameter of 30 nm. According to the invention, prepared FePO4.2H2O has the advantages of uniform particle distribution, high tap density and high reaction activity, and the primary particle is of nano grade; and FePO4.2H2O is used as a raw material so as to improve the consistency of topography of a lithium iron phosphate material, thereby effectively reducing the particle diameter of a lithium iron phosphate positive electrode material and further improving the transmission efficiency of lithium ions in the lithium iron phosphate material; and FePO4.2H2O having a micron globulomer structure, which is obtained by secondary pelleting, is more beneficial to synthesis of a micro lithium iron phosphate material which is easy to coat.

Description

A kind of iron lithium phosphate is with ball aggressiveness structure nano level preparation method of ferric phosphate
Technical field
The present invention relates to the preparation method of transition metal phosphate, be specially the nano level preparation method of ferric phosphate that can be used for preparing the phosphate metal lithium anode material.
Background technology
Iron lithium phosphate (LiFePO 4) have the removal lithium embedded function, have high energy density, cheap price, the characteristics of excellent security, being thought in the industry most possibly becomes EV positive electrode for battery material.When it has prominent advantages, also have its fatal shortcoming as EV positive electrode for battery material: electronic conductivity hangs down the magnitude at 10-9s/cm; Ion transmission efficiency hangs down the magnitude at 10-11s/cm.So low electrons/ions transmission rate makes the serious hindrance that its charge-discharge velocity improves, and has limited it in EV, the last utilization of HEV.
Current solution LiFePO 4The low problem of electrons/ions transmission rate is mainly through reducing LiFePO 4Particle diameter is realized the nanometer of material.C.Delacourt has discussed the influence of particle diameter to ion transmission efficiency at Size Effects on Carbon-Free LiFePO4 Powders The Key to Superior Energy Density (Electrochemical and Solid-State Letters, 9 (7) A352-A355).Mostly current commercially available iron lithium phosphate product is that high temperature solid-state method is synthetic, adopts common commercially available starting material to be difficult to realize the nanometer of LiFePO 4 material through the high temperature solid-state synthesis technique.
Summary of the invention
The object of the present invention is to provide a kind of nano level tertiary iron phosphate (FePO of ball aggressiveness structure 42H 2O) preparation method.This method adopts liquid phase crystallization control method technology, realizes that primary particle is nano level tertiary iron phosphate (FePO 42H 2O), for the LiFePO 4 material that adopts the synthetic high conformity of high temperature solid-state method, nanometer is laid a good foundation, through the FePO of secondary granulation gained micron order ball aggressiveness structure 42H 2O more helps the synthetic micron order LiFePO 4 material that is easy to be coated with.
To achieve these goals, the present invention adopts following technical scheme:
A kind of iron lithium phosphate comprises the steps: with ball aggressiveness structure nano level preparation method of ferric phosphate
1) will contain Fe 3+Soluble compounds with contain PO 4 3-Soluble compounds be 1 according to mass ratio: the ratio of 1-1.2 is dissolved in respectively and obtains transparent homogeneous phase solution in the deionized water, obtains mixed solution after it being mixed again;
2) will add ammonia soln in the above-mentioned mixed solution, regulate the pH value to 6-8.5;
3) will be adjusted to the neutral mixed solution places water-bath after 1-2 hour, to form white cotton-shaped suspension liquid in 50 ℃-100 ℃ heating; Obtain white filter cake after the filtration, use the deionized water wash filter cake;
4) adopt liquid phase crystallization control prepared primary particle; Spray-dried again technology is carried out secondary granulation; After spray-dried, promptly obtaining through the secondary granulation gained is that the primary particle of the 30nm back of reuniting forms the FePO that particle diameter is the spherical agglomerates micron order ball aggressiveness structure of 5-20 μ m by particle diameter 42H 2O.
Further aspect of the present invention is:
The said Fe that contains 3+Soluble compounds be Fe (NO 3) 3, Fe 2(SO 4) 3Or FeCl 3In a kind of.
The said PO that contains 4 3-Soluble compounds be H 3PO 4, (NH 4) H 2PO 4Or (NH 4) 2HPO 4In a kind of.
Use the deionized water wash filter cake in the said step 3), the conductivity value of double washing lotion differs after scouring end within 5%.
Said secondary granulation drying process adopts drying process with atomizing to realize.
Compared with prior art, the present invention has the following advantages: it is nano level tertiary iron phosphate (FePO that the present invention adopts liquid phase crystallization control prepared primary particle 42H 2O), solved the synthetic LiFePO of existing high temperature solid-state method 4Adopt conventional FePO in the process 42H 2The LiFePO that O causes 4The problem that the positive electrode material consistence is lower, be difficult to realize nanometer is through the FePO of secondary granulation gained micron order ball aggressiveness structure 42H 2O more helps the synthetic micron order LiFePO 4 material that is easy to be coated with.
The FePO that preparation method of the present invention makes 42H 2The distribution spherical in shape of O even particle size distribution, tap density is high, and primary particle is a nano level, and reactive behavior is high, and adopting should the said FePO of invention 42H 2O can improve the consistent appearance property of LiFePO 4 material as starting material, effectively reduces the particle diameter of lithium iron phosphate positive material, and then improves LiFePO 4 material lithium ion transmission efficiency, through the FePO of secondary granulation gained micron order ball aggressiveness structure 42H 2O more helps the synthetic micron order LiFePO 4 material that is easy to be coated with.
Description of drawings
Fig. 1 is SEM (scanning electronic microscope) image with embodiment 1 gained sample ball aggressiveness structure and morphology.
Fig. 2 is SEM (scanning electronic microscope) image with embodiment 1 gained sample ball aggressiveness structure primary particle pattern.
Embodiment
Through specific embodiment the present invention is done detailed description below, following embodiment only is used to illustrate the present invention, but and is not used in and limits practical range of the present invention.
Embodiment 1:
With Fe 2(SO 4) 3, H 3PO 4Be raw material, wherein PO 4 3-And Fe 3+The mass ratio of material be 1: 1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water; After above-mentioned solution mixed; Add ammonia soln; Reconcile pH to 8 back above-mentioned mixing liquid was carried out 80 ℃ of heating in water bath after 1 hour; Fully precipitate to effective constituent and to form cotton-shaped suspension liquid; Obtain white filter cake after the filtration, use the deionized water wash filter cake, the conductivity value of double washing lotion differs after scouring end within 5%; Adopt liquid phase crystallization control prepared primary particle; Spray-dried again technology is carried out secondary granulation; After spray-dried, promptly obtaining through the secondary granulation gained is that the primary particle of the 30nm back of reuniting forms the FePO that particle diameter is the spherical agglomerates micron order ball aggressiveness structure of 5-20 μ m by particle diameter 42H 2O.
SEM (scanning electronic microscope) image through embodiment 1 preparation gained sample ball aggressiveness structure and morphology is seen shown in Figure 1.SEM (scanning electronic microscope) image of gained sample ball aggressiveness structure primary particle pattern is seen shown in Figure 2.Can know by figure; Adopt liquid phase crystallization control prepared primary particle; Spray-dried again technology is carried out secondary granulation; Solved the problem that current commercially available iron lithium phosphate product high temperature solid-state method synthesis technique is difficult to the nanometer of realization LiFePO 4 material; Its particle structure pattern has been realized nanometer, has solved LiFePO 4The problem that electronic conductivity is low, ion transmission efficiency is low.
Embodiment 2:
With Fe (NO 3) 3, H 3PO 4Be raw material, wherein PO 4 3-And Fe 3+The amount of substance ratio be 1: 1.1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water; After above-mentioned solution mixed; Add ammonia soln; Reconciling pH to 7 back carries out 60 ℃ of heating in water bath to above-mentioned mixing liquid and fully precipitates to effective constituent after 2 hours and form cotton-shaped suspension liquid; Obtain white filter cake after the filtration; Use the deionized water wash filter cake, the conductivity value of double washing lotion differs after scouring end within 5%; Adopt liquid phase crystallization control prepared primary particle; Spray-dried again technology is carried out secondary granulation; After spray-dried, promptly obtaining through the secondary granulation gained is that the primary particle of the 30nm back of reuniting forms the FePO that particle diameter is the spherical agglomerates micron order ball aggressiveness structure of 5-20 μ m by particle diameter 42H 2O.
Embodiment 3:
With FeCl 3, H 3PO 4Be raw material, wherein PO 4 3-And Fe 3+The mass ratio of material be 1: 1.2.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water; After above-mentioned solution mixed; Add ammonia soln; Reconciling pH to 8.5 back carries out 100 ℃ of heating in water bath to above-mentioned mixing liquid and fully precipitates to effective constituent after 1.5 hours and form cotton-shaped suspension liquid; Obtain white filter cake after the filtration; Use the deionized water wash filter cake, the conductivity value of double washing lotion differs after scouring end within 5%; Adopt liquid phase crystallization control prepared primary particle; Spray-dried again technology is carried out secondary granulation; After spray-dried, promptly obtaining through the secondary granulation gained is that the primary particle of the 30nm back of reuniting forms the FePO that particle diameter is the spherical agglomerates micron order ball aggressiveness structure of 5-20 μ m by particle diameter 42H 2O.
Embodiment 4:
With Fe 2(SO 4) 3, (NH 4) H 2PO 4Be raw material, wherein PO 4 3-And Fe 3+The mass ratio of material be 1: 1.1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water; After above-mentioned solution mixed; Add ammonia soln; Reconciling pH to 8 back carries out 50 ℃ of heating in water bath to above-mentioned mixing liquid and fully precipitates to effective constituent after 1 hour and form cotton-shaped suspension liquid; Obtain white filter cake after the filtration; Use the deionized water wash filter cake, the conductivity value of double washing lotion differs after scouring end within 5%; Adopt liquid phase crystallization control prepared primary particle; Spray-dried again technology is carried out secondary granulation; After spray-dried, promptly obtaining through the secondary granulation gained is that the primary particle of the 30nm back of reuniting forms the FePO that particle diameter is the spherical agglomerates micron order ball aggressiveness structure of 5-20 μ m by particle diameter 42H 2O.
Embodiment 5:
With Fe 2(SO 4) 3, (NH 4) 2HPO 4Be raw material, wherein PO 4 3-And Fe 3+The mass ratio of material be 1: 1.2.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water; After above-mentioned solution mixed; Add ammonia soln; Reconciling pH to 6 back carries out 90 ℃ of heating in water bath to above-mentioned mixing liquid and fully precipitates to effective constituent after 1 hour and form cotton-shaped suspension liquid; Obtain white filter cake after the filtration; Use the deionized water wash filter cake, the conductivity value of double washing lotion differs after scouring end within 5%; Adopt liquid phase crystallization control prepared primary particle; Spray-dried again technology is carried out secondary granulation; After spray-dried, promptly obtaining through the secondary granulation gained is that the primary particle of the 30nm back of reuniting forms the FePO that particle diameter is the spherical agglomerates micron order ball aggressiveness structure of 5-20 μ m by particle diameter 42H 2O.
Embodiment 6:
With FeCl 3, (NH 4) H 2PO 4Be raw material, wherein PO 4 3-And Fe 3+The mass ratio of material be 1: 1.1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water; After above-mentioned solution mixed; Add ammonia soln; Reconciling pH to 8.5 back carries out 100 ℃ of heating in water bath to above-mentioned mixing liquid and fully precipitates to effective constituent after 1.5 hours and form cotton-shaped suspension liquid; Obtain white filter cake after the filtration; Use the deionized water wash filter cake, the conductivity value of double washing lotion differs after scouring end within 5%; Adopt liquid phase crystallization control prepared primary particle; Spray-dried again technology is carried out secondary granulation; After spray-dried, promptly obtaining through the secondary granulation gained is that the primary particle of the 30nm back of reuniting forms the FePO that particle diameter is the spherical agglomerates micron order ball aggressiveness structure of 5-20 μ m by particle diameter 42H 2O.

Claims (4)

1. an iron lithium phosphate is characterized in that with ball aggressiveness structure nano level preparation method of ferric phosphate, comprises the steps:
1) will contain Fe 3+Soluble compounds with contain PO 4 3-Soluble compounds be 1 according to mass ratio: the ratio of 1-1.2 is dissolved in respectively and obtains transparent homogeneous phase solution in the deionized water, obtains mixed solution after it being mixed again;
2) will add ammonia soln in the above-mentioned mixed solution, regulate the pH value to 6-8.5;
3) will be adjusted to the neutral mixed solution places water-bath after 1-2 hour, to form white cotton-shaped suspension liquid in 50 ℃-100 ℃ heating; Obtain white filter cake after the filtration, use the deionized water wash filter cake;
4) adopt liquid phase crystallization control prepared primary particle; Spray-dried again technology is carried out secondary granulation; After spray-dried, promptly obtaining through the secondary granulation gained is that the primary particle of the 30nm back of reuniting forms the FePO that particle diameter is the spherical agglomerates micron order ball aggressiveness structure of 5-20 μ m by particle diameter 42H 2O.
2. a kind of according to claim 1 iron lithium phosphate is characterized in that: the said Fe of containing with ball aggressiveness structure nano level preparation method of ferric phosphate 3+Soluble compounds be Fe (NO 3) 3, Fe 2(SO 4) 3Or FeCl 3In a kind of.
3. a kind of according to claim 1 iron lithium phosphate is characterized in that: the said PO of containing with ball aggressiveness structure nano level preparation method of ferric phosphate 4 3-Soluble compounds be H 3PO 4, (NH 4) H 2PO 4Or (NH 4) 2HPO 4In a kind of.
4. a kind of according to claim 1 iron lithium phosphate is characterized in that with ball aggressiveness structure nano level preparation method of ferric phosphate: use the deionized water wash filter cake in the said step 3), the conductivity value of double washing lotion differs after scouring end within 5%.
CN201110201227A 2011-07-19 2011-07-19 Preparation method of nano iron phosphate with globulomer structure for lithium iron phosphate Pending CN102303857A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110201227A CN102303857A (en) 2011-07-19 2011-07-19 Preparation method of nano iron phosphate with globulomer structure for lithium iron phosphate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110201227A CN102303857A (en) 2011-07-19 2011-07-19 Preparation method of nano iron phosphate with globulomer structure for lithium iron phosphate

Publications (1)

Publication Number Publication Date
CN102303857A true CN102303857A (en) 2012-01-04

Family

ID=45377801

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110201227A Pending CN102303857A (en) 2011-07-19 2011-07-19 Preparation method of nano iron phosphate with globulomer structure for lithium iron phosphate

Country Status (1)

Country Link
CN (1) CN102303857A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104362341A (en) * 2014-09-23 2015-02-18 深圳市贝特瑞新能源材料股份有限公司 High-density nano-lithium iron phosphate material and preparation method thereof
CN106564867A (en) * 2016-10-09 2017-04-19 华南理工大学 Method for preparing iron phosphate material by adding reducing organic matters
CN111115606A (en) * 2020-02-25 2020-05-08 瓮福（集团）有限责任公司 Preparation method for preparing superfine spherical iron phosphate by combining liquid-phase precipitation with spray drying

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101877401A (en) * 2010-06-30 2010-11-03 彩虹集团公司 Method for preparing lithium-ion battery anode material LiFePO4

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101877401A (en) * 2010-06-30 2010-11-03 彩虹集团公司 Method for preparing lithium-ion battery anode material LiFePO4

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
从长杰 等: "纳米磷酸铁锂的制备及电化学性能研究", 《无机化学学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104362341A (en) * 2014-09-23 2015-02-18 深圳市贝特瑞新能源材料股份有限公司 High-density nano-lithium iron phosphate material and preparation method thereof
CN106564867A (en) * 2016-10-09 2017-04-19 华南理工大学 Method for preparing iron phosphate material by adding reducing organic matters
CN111115606A (en) * 2020-02-25 2020-05-08 瓮福（集团）有限责任公司 Preparation method for preparing superfine spherical iron phosphate by combining liquid-phase precipitation with spray drying

Similar Documents

Publication Publication Date Title
CN101859891B (en) Lithium battery electrode material
CN101924205B (en) Method for preparing electrode material of lithium battery
NZ528727A (en) Binary, ternary and quaternary lithium phosphates, method for the production thereof and use of the same
CN103708434B (en) LiFePO 4 material and preparation method thereof
CN101891176B (en) Method for preparing iron phosphate by using nonionic surfactant
CN101269807A (en) High-density spherical iron phosphate and manufacture method thereof
CN102556994B (en) Preparation method of nanoscale iron phosphate
CN112436132B (en) Method for preparing in-situ carbon-coated porous ferric phosphate material by adopting sweet osmanthus
CN105576217A (en) Preparation method of three-dimensional carbon in-situ coated phosphate positive electrode material
CN103078114A (en) Porous lithium iron phosphate/carbon composite microspheres and preparation method thereof
CN102280621A (en) Method for preparing lithium ion battery material lithium and manganese phosphate/carbon by adopting sol-gel method
CN105449208A (en) Spherical micro-nano ferric phosphate/carbon composite material and preparation method thereof
CN102616763B (en) Preparation method of iron phosphate for preparing lithium iron phosphate and iron phosphate
CN106169567B (en) A kind of carbon-coated lithium iron phosphate positive material and preparation method thereof
CN103682271B (en) The preparation method of multilayer shell-core structural lithium ion battery
CN108565459A (en) A kind of method that iron oxide modified prepares LiFePO4
CN102074690B (en) Method for synthesizing battery anode material LiFePO4 by using controllable carbon clad FePO4
CN106981656A (en) Preparation method of battery-grade ferromanganese phosphate
CN102303857A (en) Preparation method of nano iron phosphate with globulomer structure for lithium iron phosphate
CN107253706A (en) The preparation method of form iron phosphate crystal with nanometer sheet-micron ball secondary structure
CN105645371A (en) One-step preparation method and application of nano transition metal phosphates
CN104085868B (en) The preparation method of a kind of 3D micro-nano structure spherical active phosphorus acid iron
CN101913585A (en) Synthesizing method of battery-level ultra-thin iron phosphate
CN101867042A (en) Preparation method of nanometer level metallic lithium phosphate salt LiMPO4
CN102303858A (en) Preparation method of nanoscale ferric phosphate for lithium iron phosphate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20120104