CN104852046A - Nanometer piece shaped LMFP material, and manufacturing method and application thereof - Google Patents

Nanometer piece shaped LMFP material, and manufacturing method and application thereof Download PDF

Info

Publication number
CN104852046A
CN104852046A CN201510163036.6A CN201510163036A CN104852046A CN 104852046 A CN104852046 A CN 104852046A CN 201510163036 A CN201510163036 A CN 201510163036A CN 104852046 A CN104852046 A CN 104852046A
Authority
CN
China
Prior art keywords
solution
ethylene glycol
lioh
nano
life
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.)
Granted
Application number
CN201510163036.6A
Other languages
Chinese (zh)
Other versions
CN104852046B (en
Inventor
赵新兵
廖龙欢
谢健
曹高劭
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.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
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 Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN201510163036.6A priority Critical patent/CN104852046B/en
Publication of CN104852046A publication Critical patent/CN104852046A/en
Application granted granted Critical
Publication of CN104852046B publication Critical patent/CN104852046B/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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention discloses a nanometer piece shaped LMFP material, which consists of LiFe0.1Mn0.9PO4 of a piece shaped structure, and Fe is evenly distributed at a crystal lattice position of Mn; and LiFe0.1Mn0.9PO4 of the piece shaped structure is in a shape of a cuboid with a nanoscale size, wherein the sizes of the length and the width are both less than 100 nanometers, and the thickness is less than 20 nanometers. The material of the present invention can be prepared to be a LiFe0.1Mn0.9PO4 material having a nanometer piece shaped structure and LiFePO4/LiMnPO4 being a solid solution via a small amount of iron for doping (10%) through an optimum synthesis process; moreover, the material has an outstanding large current cycling stability and rate capability. The manufacturing method has a simple and controllable process, a low power consumption, and a low cost, and is suitable for large-scale industrial productions.

Description

Nano-sheet iron manganese phosphate lithium material and its preparation method and application
Technical field
The present invention relates to the technical field of anode material for lithium ion battery, particularly relate to a kind of nano-sheet iron manganese phosphate lithium material and its preparation method and application.
Background technology
Lithium ion battery has the advantages such as operating voltage is high, energy density is large, security performance is good, therefore be used widely in the portable type electronic products such as digital camera, mobile phone and notebook computer, also there is application prospect for electric bicycle and electric automobile.Current commercial lithium ion battery generally adopts cobalt acid lithium (LiCoO 2), LiMn2O4 (LiMn 2o 4), LiFePO4 (LiFePO 4) as positive electrode.In above-mentioned material, LiFePO 4material, due to the advantage such as its safety, environmental protection, price be low, has been used as the positive electrode of electric vehicle battery at present.But the operating voltage of this material is lower, only has 3.5V, and is all the LiMnPO of olive-type structure 4operating voltage is then 4.1V, has higher energy density, has tempting application prospect, therefore receive much concern in recent years in electric automobile.But with LiFePO 4compare, LiMnPO 4electronic conductivity and lithium ion diffusion rate lower, cause its chemical property poor, the cyclical stability particularly under high rate performance and big current is poor.
Research in recent years finds, part Mn Fe is replaced (LiFe xmn 1 – xpO 4), can LiMnPO be significantly improved 4chemical property, and a small amount of Fe doping is to LiMnPO 4energy density impact little.
As the publication number Chinese patent literature that is CN104466161A discloses a kind of solid phase synthesis process of iron manganese phosphate lithium material; after persursor material source of iron, lithium source, phosphorus source, manganese source are mixed in proportion; add dispersant and carry out ball milling, oven dry; under nitrogen protection atmosphere, carry out once sintered, double sintering respectively, finally obtain LiMn xfe 1-xpO 4material.
And for example, publication number is the hydrothermal preparing process that the Chinese patent literature of CN103762362A discloses a kind of nano lithium iron manganese phosphate anode material, prepares presoma: in molar ratio for Li:P=3:1 is by H 3pO 4solution and LiOHH 2o mixes; Add concentrated ammonia liquor, pH value 9 ~ 10; Be warming up to 180 DEG C, (Fe+Mn): Ti:P=0.99:0.01:1 adds in deionized water in molar ratio, and mixed solution pumps in reactor, and regulating and controlling temperature is at 170 ~ 200 DEG C; Be heated to 200 DEG C of insulation 7 ~ 10h; Washing and carbon coated; When being cooled to less than 60 DEG C, spending deionized water to sulfate radical-free, adding dissolved organic matter carbon source, spraying dry, heat treatment 7 ~ 10h, obtains LiMn after cooling xfe 0.99-xti 0.01pO 4powder.
But the iron manganese phosphate lithium material adopting said method to prepare still faces the challenge, and one of them shortcoming is structural instability, very fast through repeated charge capacity attenuation, and high rate performance is also not ideal enough.
Summary of the invention
The present invention by a small amount of doping (10%) of iron, and by optimum synthesis technique, prepares the structure with nano-sheet, and LiFePO 4/ LiMnPO 4liFe in solid solution 0.1mn 0.9pO 4material, this material has excellent big current cyclical stability and high rate performance.This preparation method's technique is simply controlled, and energy consumption is low, cost is low, is suitable for large-scale industrial production.
A kind of nano-sheet iron manganese phosphate lithium material, by the LiFe of laminated structure 0.1mn 0.9pO 4composition, and Fe is uniformly distributed at the lattice position of Mn, the LiFe of described laminated structure 0.1mn 0.9pO 4present cuboid, be of a size of nanoscale, long and wide size is all less than 100 nanometers, and thickness is less than 20 nanometers.
As preferably, the LiFe of described laminated structure 0.1mn 0.9pO 4length and be widely of a size of 40 ~ 100 nanometers, thickness is 10 ~ 20 nanometers.
The LiFe of this laminated structure 0.1mn 0.9pO 4in, Fe is uniformly distributed at the lattice position of Mn, i.e. LiFe 0.1mn 0.9pO 4middle LiFePO 4/ LiMnPO 4in solid solution condition.Due to flaky nanometer structure and the LiFePO of its uniqueness 4/ LiMnPO 4solid solution, be conducive to electrical conductivity, the embedding/deviate from of lithium ion, the infiltration of electrolyte and the stability of structure.
The invention also discloses the preparation method of described nano-sheet iron manganese phosphate lithium material, comprise the following steps:
1) LiOH/ ethylene glycol solution I and H is prepared respectively 3pO 4/ ethylene glycol solution I, obtains suspension a1 after mixing; By MnSO 4mix with the mixed solvent of ethylene glycol/deionized water, obtain solution b1; Again solution b1 is dropwise instilled in solution a1, stir and obtain solution c1;
2) LiOH/ ethylene glycol solution II and H is prepared respectively 3pO 4/ ethylene glycol solution II, obtains suspension a2 after mixing; By FeSO 4mix with ethylene glycol, obtain solution b2; Again solution b2 is dropwise instilled in solution a2, stir and obtain solution c2;
3) solution c2 is dropwise instilled in solution c1, stir and obtain precursor solution, obtain described nano-sheet iron manganese phosphate lithium material through solvent thermal reaction and reprocessing.
The present invention prepares synthesis LiMnPO respectively 4and LiFePO 4precursor solution, then solvent thermal reaction is carried out in both mixing, is obtained the LiFe of flake nano structure by the optimized fabrication of this preparation technology 0.1mn 0.9pO 4material, is conducive to forming LiFePO 4/ LiMnPO 4solid-solution structures, and be conducive to suppressing LiFe 0.1mn 0.9pO 4growing up of crystal grain, utilizes flaky nanometer structure and LiFePO 4/ LiMnPO 4solid solution can significantly improve LiFe 0.1mn 0.9pO 4electronic conductivity, lithium ion diffusion rate and structural stability, thus improve LiFe 0.1mn 0.9pO 4the chemical property of material, particularly big current cyclical stability and high rate performance are LiFe 0.1mn 0.9pO 4the raising of material electrochemical performance opens a kind of new way.And adopt conventional one kettle way preparation synthesis LiFe 0.1mn 0.9pO 4presoma when carrying out solvent thermal reaction, then can cause LiFe 0.1mn 0.9pO 4growing up and LiFePO of crystal grain 4/ LiMnPO 4phase-splitting, cause the deterioration of chemical property.
As preferably, step 1) in, the molar concentration of described LiOH/ ethylene glycol solution I is 1 ~ 4mol/L, MnSO 4, H 3pO 4be 1:1.1 ~ 1.16:3 with the mol ratio of LiOH.Preferably the molar concentration of LiOH/ ethylene glycol solution I is 2 ~ 3mol/L further, and concentration is too low is unfavorable for LiFe 0.1mn 0.9pO 4crystallization, excessive concentration will cause insufficient dissolving of LiOH and the incomplete of chemical reaction.
As preferably, step 1) in, in described mixed solvent, the volume ratio of ethylene glycol and deionized water is 1:1;
Described LiOH/ ethylene glycol solution I, H 3pO 4/ ethylene glycol solution I is 1:1:1 with the volume ratio of solution b1.
As preferably, step 2) in, the molar concentration of described LiOH/ ethylene glycol solution II is 1/9, H of the molar concentration of LiOH/ ethylene glycol solution I 3pO 4the molar concentration of/ethylene glycol solution II is H 3pO 41/9, FeSO in solution b2 of the molar concentration of/ethylene glycol solution I 4molar concentration be MnSO in solution b1 4molar concentration 1/9;
Described LiOH/ ethylene glycol solution II, H 3pO 4the volume ratio of/ethylene glycol solution II and solution b2 is 1:1:1.
As preferably, step 3) in, solution c1 mixes with solution c2 equal-volume.
As preferably, step 3) in, described solvent thermal reaction reacts 6 ~ 9h at 140 ~ 170 DEG C.Further preferably, solvent thermal reaction reacts 8 ~ 9h at 160 ~ 170 DEG C.Find after deliberation, reaction temperature is higher, and the time is longer, LiFe 0.1mn 0.9pO 4crystallinity better, but too high temperature (as>=180 DEG C) and long reaction time (as>=10h) will LiFe be caused 0.1mn 0.9pO 4obviously growing up of crystal grain, thus the deterioration causing chemical property.
Described reprocessing comprises cooling precipitation, centrifugal and dry, and the restriction that chilling temperature is not strict, based on adequate operation, generally can be cooled to the ambient temperature of 15 ~ 30 DEG C.
The LiFe of the above-mentioned laminated structure prepared 0.1mn 0.9pO 4material, its chemical property is good, and particularly big current cyclical stability and high rate performance, therefore, can be used as or prepare anode material for lithium-ion batteries.
Compared with prior art, tool of the present invention has the following advantages:
1, the present invention adopts low temperature liquid polymerization process to prepare LiFe 0.1mn 0.9pO 4material, has that technique is simply controlled, cost is low, the cycle is short, energy consumption is low and the advantage such as applicable suitability for industrialized production.
2, the LiFe for preparing of the present invention 0.1mn 0.9pO 4material, due to nanostructure in the form of sheets, is conducive to electrical conductivity, the embedding/deviate from of lithium ion, the infiltration of electrolyte, is therefore conducive to the raising of the special high rate performance of chemical property of material.
3, the LiFe for preparing of the present invention 0.1mn 0.9pO 4material, due to structure and LiFePO in the form of sheets 4/ LiMnPO 4solid-solution structures, in charge and discharge process, embody higher structural stability, therefore there is higher cyclical stability particularly big current cyclical stability, can be used as or prepare anode material for lithium-ion batteries.
Accompanying drawing explanation
Fig. 1 is LiFe prepared by embodiment 1 0.1mn 0.9pO 4the X ray diffracting spectrum of material;
Fig. 2 is LiFe prepared by embodiment 1 0.1mn 0.9pO 4the scanning electron microscope (SEM) photograph of material;
Fig. 3 is LiFe prepared by embodiment 1 0.1mn 0.9pO 4the transmission electron microscope picture of material;
Fig. 4 is LiFe prepared by embodiment 1 0.1mn 0.9pO 4the distribution diagram of element of middle Mn and Fe;
Fig. 5 is respectively with LiFe prepared by embodiment 1 (A), comparative example 1 (B) 0.1mn 0.9pO 4material is the chemical property figure of the lithium ion battery of positive electrode assembling;
A figure is cycle performance figure, b figure is high rate performance figure;
Fig. 6 is LiFe prepared by comparative example 1 0.1mn 0.9pO 4the scanning electron microscope (SEM) photograph of material.
Embodiment
Embodiment 1
0.027mol LiOH is dissolved in 10mL ethylene glycol, stirs, obtain the LiOH solution that concentration is 2.7mol/L, by 0.0099mol H 3pO 4be dissolved in 10mL ethylene glycol, stir, obtain H 3pO 4solution, then by H 3pO 4dropwise joins in LiOH solution, stirs, and obtains suspension a1; By 0.009mol MnSO 4be dissolved in the mixed solvent of 5mL ethylene glycol and 5mL deionized water, obtain solution b1, then b1 is dropwise instilled in a1, stir, obtain solution c1; 0.003mol LiOH is dissolved in 10mL ethylene glycol, stirs, obtain LiOH solution, by 0.0011mol H 3pO 4be dissolved in 10mL ethylene glycol, stir, obtain H 3pO 4solution, then by H 3pO 4dropwise joins in LiOH solution, stirs, and obtains suspension a2; By 0.001mol FeSO 4be dissolved in 10mL ethylene glycol, obtain solution b2, then b2 is dropwise instilled in a2, stir, obtain solution c2; C2 is dropwise instilled in c1, stirs, obtain precursor solution, then precursor solution is sealed in reactor, react 9 hours at 170 DEG C, be precipitated through cooling, then through centrifugal, dry, obtain LiFe 0.1mn 0.9pO 4nanometer sheet.
The X ray diffracting spectrum of resulting materials, scanning electron microscope (SEM) photograph, and transmission electron microscope picture is respectively as Fig. 1, Fig. 2 and Fig. 3, wherein the diffraction maximum of X ray can be summed up as LiFe 0.1mn 0.9pO 4.Know from ESEM and transmission electron microscope, resulting materials presents laminated structure, and presents cuboid, and it is long and wide is 40 ~ 100 nanometers, and thickness is 10 ~ 20 nanometers.The Elemental redistribution of Mn and Fe of resulting materials is shown in Fig. 4, and from figure, Fe element is dispersed in Mn lattice, i.e. LiFePO 4/ LiMnPO 4in solid solution state.
LiFe 0.1mn 0.9pO 4material, before carrying out electro-chemical test, first carries out the coated process of carbon (by LiFe 0.1mn 0.9pO 4with glucose 2:1 mixing in mass ratio, under 600 DEG C of argon atmosphers, reaction obtains LiFe in 4 hours 0.1mn 0.9pO 4/ C compound, compound carbon containing 9wt%, and keep sheet nanostructure).By LiFe coated for gained carbon 0.1mn 0.9pO 4nanometer sheet carries out electrochemical property test (constant current charge-discharge within the scope of certain voltage) as anode material for lithium-ion batteries, the cycle performance figure of resulting materials is as Fig. 5 a (curve A), constant current charge-discharge (current density 1C=170mA/g, voltage range 2 ~ 4.5V) test show, when cycle-index is 1, the LiFe that carbon is coated 0.1mn 0.9pO 4the capacity of nanometer sheet is 140mAh/g, and when cycle-index is 100, the capacity of this material still remains on 130mAh/g, demonstrates higher capacity and good cycle performance.The high rate performance figure of resulting materials is as Fig. 5 b (curve A), and from figure, this material has excellent high rate performance equally, and when 10C, capacity is still close to 120mAh/g.
Comparative example 1
Adopt one kettle way preparation synthesis LiFe 0.1mn 0.9pO 4precursor solution.0.03mol LiOH is dissolved in 20mL ethylene glycol, stirs, obtain the LiOH solution that concentration is 3mol/L, by 0.011mol H 3pO 4be dissolved in 20mL ethylene glycol, stir, obtain H 3pO 4solution, then by H 3pO 4dropwise joins in LiOH solution, stirs, and obtains suspension a3; By 0.009mol MnSO 4with 0.001mol FeSO 4be dissolved in the mixed solvent of 15mL ethylene glycol and 5mL deionized water, obtain solution b3, then b3 is dropwise instilled in a3, stir, obtain solution c3; Again precursor solution is sealed in reactor, reacts 9 hours at 170 DEG C, be precipitated through cooling, then through centrifugal, dry, obtain LiFe 0.1mn 0.9pO 4nanometer sheet.
The X ray diffracting spectrum of resulting materials can be summed up as LiFe 0.1mn 0.9pO 4, from the stereoscan photograph of Fig. 6, resulting materials presents irregularly shaped, and most of particle size is greater than 100 nanometers, and thickness is greater than 20 nanometers.The element distribution analysis of Mn and Fe shows, i.e. LiFePO 4/ LiMnPO 4present phase separation structure.
To above-mentioned gained LiFe 0.1mn 0.9pO 4nanometer sheet carries out similar bag carbon and electro-chemical test, and test result shows, the LiFe prepared by this technique 0.1mn 0.9pO 4chemical property obviously to be inferior to embodiment 1.When 1C constant current charge-discharge, when cycle-index is 1, the LiFe that carbon is coated 0.1mn 0.9pO 4the capacity of nanometer sheet is 118mAh/g, and when cycle-index is 100, the capacity of this material is only 102mAh/g, sees Fig. 5 a (curve B).The high rate performance figure of resulting materials is as Fig. 5 b (curve B), and from figure, when 10C, capacity is only 71mAh/g.As can be seen here, presoma preparing process during synthesis affects structure and the chemical property of product.Also illustrate, synthesis technique of the present invention has reasonability simultaneously.
Comparative example 2
The method of embodiment 1 prepares plain LiMnPO 4, namely in the process of preparation b2 solution, do not use FeSO 4, and use MnSO 4, the mixed solvent that the solvent of use is 5mL ethylene glycol and 5mL deionized water, other steps are identical.Similar method is adopted to carry out the coated and electro-chemical test of carbon.The sheet LiMnPO of pure phase can be prepared by the method 4, and in cuboid, it is long and wide is 40 ~ 100 nanometers, and thickness is 10 ~ 20 nanometers.Electro-chemical test shows, the LiMnPO that carbon is coated 4cyclical stability and high rate performance be all inferior to the LiMnPO that Fe adulterates 4.This illustrates that doped F e can improve LiMnPO 4cyclical stability and high rate performance.
Embodiment 2
By 0.027mol LiOHH 2o is dissolved in 10mL ethylene glycol, stirs, and obtains the LiOH solution that concentration is 2.7mol/L, by 0.01008mol H 3pO 4be dissolved in 10mL ethylene glycol, stir, obtain H 3pO 4solution, then by H 3pO 4dropwise joins in LiOH solution, stirs, and obtains suspension a1; By 0.009mol MnSO 4be dissolved in the mixed solvent of 5mL ethylene glycol and 5mL deionized water, obtain solution b1, then b1 is dropwise instilled in a1, stir, obtain solution c1; By 0.003mol LiOHH 2o is dissolved in 10mL ethylene glycol, stirs, and obtains LiOH solution, by 0.00112mol H 3pO 4be dissolved in 10mL ethylene glycol, stir, obtain H 3pO 4solution, then by H 3pO 4dropwise joins in LiOH solution, stirs, and obtains suspension a2; By 0.001mol FeSO 4be dissolved in 10mL ethylene glycol, obtain solution b2, then b2 is dropwise instilled in a2, stir, obtain solution c2; C2 is dropwise instilled in c1, stirs, obtain precursor solution, then precursor solution is sealed in reactor, react 8 hours at 160 DEG C, be precipitated through cooling, then through centrifugal, dry, obtain LiFe 0.1mn 0.9pO 4nanometer sheet.
The diffraction maximum of the X ray of resulting materials can be summed up as LiFe 0.1mn 0.9pO 4.Know from ESEM and transmission electron microscope, resulting materials presents laminated structure, and presents cuboid, and it is long and wide is 40 ~ 100 nanometers, and thickness is 10 ~ 20 nanometers.The Elemental redistribution of Mn and Fe of resulting materials is known, and Fe element is dispersed in Mn lattice, i.e. LiFePO 4/ LiMnPO 4in solid solution state.
LiFe 0.1mn 0.9pO 4material, before carrying out electro-chemical test, first carries out the coated process of carbon (by LiFe 0.1mn 0.9pO 4with glucose 2:1 mixing in mass ratio, under 600 DEG C of argon atmosphers, reaction obtains LiFe in 4 hours 0.1mn 0.9pO 4/ C compound, compound carbon containing 9wt%, and keep sheet nanostructure).By LiFe coated for gained carbon 0.1mn 0.9pO 4nanometer sheet carries out electrochemical property test (constant current charge-discharge within the scope of certain voltage) as anode material for lithium-ion batteries, constant current charge-discharge (current density 1C=170mA/g, voltage range 2 ~ 4.5V) test show, when cycle-index is 1, the LiFe that carbon is coated 0.1mn 0.9pO 4the capacity of nanometer sheet is 138mAh/g, and when cycle-index is 100, the capacity of this material still remains on 126mAh/g, demonstrates higher capacity and good cycle performance.The multiplying power test of resulting materials shows, this material has excellent high rate performance equally and exists, and during 10C, capacity is still close to 120mAh/g.
Embodiment 3
By 0.027mol LiOHH 2o is dissolved in 10mL ethylene glycol, stirs, and obtains the LiOH solution that concentration is 2.7mol/L, by 0.01026mol H 3pO 4be dissolved in 10mL ethylene glycol, stir, obtain H 3pO 4solution, then by H 3pO 4dropwise joins in LiOH solution, stirs, and obtains suspension a1; By 0.009mol MnSO 4h 2o is dissolved in the mixed solvent of 5mL ethylene glycol and 5mL deionized water, obtains solution b1, is more dropwise instilled in a1 by b1, stirs, and obtains solution c1; By 0.003mol LiOHH 2o is dissolved in 10mL ethylene glycol, stirs, and obtains LiOH solution, by 0.00114mol H 3pO 4be dissolved in 10mL ethylene glycol, stir, obtain H 3pO 4solution, then by H 3pO 4dropwise joins in LiOH solution, stirs, and obtains suspension a2; By 0.001mol FeSO 4be dissolved in 10mL ethylene glycol, obtain solution b2, then b2 is dropwise instilled in a2, stir, obtain solution c2; C2 is dropwise instilled in c1, stirs, obtain precursor solution, then precursor solution is sealed in reactor, react 8.5 hours at 165 DEG C, be precipitated through cooling, then through centrifugal, dry, obtain LiFe 0.1mn 0.9pO 4nanometer sheet.
The diffraction maximum of the X ray of resulting materials can be summed up as LiFe 0.1mn 0.9pO 4.Know from ESEM and transmission electron microscope, resulting materials presents laminated structure, and presents cuboid, and it is long and wide is 40 ~ 100 nanometers, and thickness is 10 ~ 20 nanometers.The Elemental redistribution of Mn and Fe of resulting materials is known, and Fe element is dispersed in Mn lattice, i.e. LiFePO 4/ LiMnPO 4in solid solution state.
LiFe 0.1mn 0.9pO 4material, before carrying out electro-chemical test, first carries out the coated process of carbon (by LiFe 0.1mn 0.9pO 4with glucose 2:1 mixing in mass ratio, under 600 DEG C of argon atmosphers, reaction obtains LiFe in 4 hours 0.1mn 0.9pO 4/ C compound, compound carbon containing 9wt%, and keep sheet nanostructure).By LiFe coated for gained carbon 0.1mn 0.9pO 4nanometer sheet carries out electrochemical property test (constant current charge-discharge within the scope of certain voltage) as anode material for lithium-ion batteries, constant current charge-discharge (current density 1C=170mA/g, voltage range 2 ~ 4.5V) test show, when cycle-index is 1, the LiFe that carbon is coated 0.1mn 0.9pO 4the capacity of nanometer sheet is 137mAh/g, and when cycle-index is 100, the capacity of this material still remains on 128mAh/g, demonstrates higher capacity and good cycle performance.The multiplying power test of resulting materials shows, this material has excellent high rate performance equally and exists, and during 10C, capacity is still close to 120mAh/g.
Embodiment 4
0.027mol LiOH is dissolved in 10mL ethylene glycol, stirs, obtain the LiOH solution that concentration is 2.7mol/L, by 0.01044mol H 3pO 4be dissolved in 10mL ethylene glycol, stir, obtain H 3pO 4solution, then by H 3pO 4dropwise joins in LiOH solution, stirs, and obtains suspension a1; By 0.009mol MnSO 4h 2o is dissolved in the mixed solvent of 5mL ethylene glycol and 5mL deionized water, obtains solution b1, is more dropwise instilled in a1 by b1, stirs, and obtains solution c1; 0.003mol LiOH is dissolved in 10mL ethylene glycol, stirs, obtain LiOH solution, by 0.00116mol H 3pO 4be dissolved in 10mL ethylene glycol, stir, obtain H 3pO 4solution, then by H 3pO 4dropwise joins in LiOH solution, stirs, and obtains suspension a2; By 0.001mol FeSO 47H 2o is dissolved in 10mL ethylene glycol, obtains solution b2, is more dropwise instilled in a2 by b2, stirs, and obtains solution c2; C2 is dropwise instilled in c1, stirs, obtain precursor solution, then precursor solution is sealed in reactor, react 8 hours at 170 DEG C, be precipitated through cooling, then through centrifugal, dry, obtain LiFe 0.1mn 0.9pO 4nanometer sheet.
The diffraction maximum of the X ray of resulting materials can be summed up as LiFe 0.1mn 0.9pO 4.Know from ESEM and transmission electron microscope, resulting materials presents laminated structure, and presents cuboid, and it is long and wide is 40 ~ 100 nanometers, and thickness is 10 ~ 20 nanometers.The Elemental redistribution of Mn and Fe of resulting materials is known, and Fe element is dispersed in Mn lattice, i.e. LiFePO 4/ LiMnPO 4in solid solution state.
LiFe 0.1mn 0.9pO 4material, before carrying out electro-chemical test, first carries out the coated process of carbon (by LiFe 0.1mn 0.9pO 4with glucose 2:1 mixing in mass ratio, under 600 DEG C of argon atmosphers, reaction obtains LiFe in 4 hours 0.1mn 0.9pO 4/ C compound, compound carbon containing 9wt%, and keep sheet nanostructure).By LiFe coated for gained carbon 0.1mn 0.9pO 4nanometer sheet carries out electrochemical property test (constant current charge-discharge within the scope of certain voltage) as anode material for lithium-ion batteries, constant current charge-discharge (current density 1C=170mA/g, voltage range 2 ~ 4.5V) test show, when cycle-index is 1, the LiFe that carbon is coated 0.1mn 0.9pO 4the capacity of nanometer sheet is 141mAh/g, and when cycle-index is 100, the capacity of this material still remains on 131mAh/g, demonstrates higher capacity and good cycle performance.The multiplying power test of resulting materials shows, this material has excellent high rate performance equally and exists, and during 10C, capacity is still close to 120mAh/g.

Claims (9)

1. a nano-sheet iron manganese phosphate lithium material, is characterized in that, by the LiFe of laminated structure 0.1mn 0.9pO 4composition, and Fe is uniformly distributed at the lattice position of Mn, the LiFe of described laminated structure 0.1mn 0.9pO 4present cuboid, be of a size of nanoscale, long and wide size is all less than 100 nanometers, and thickness is less than 20 nanometers.
2. nano-sheet iron manganese phosphate lithium material according to claim 1, is characterized in that, the LiFe of described laminated structure 0.1mn 0.9pO 4length and be widely of a size of 40 ~ 100 nanometers, thickness is 10 ~ 20 nanometers.
3. a preparation method for nano-sheet iron manganese phosphate lithium material according to claim 1, is characterized in that, comprise the following steps:
1) LiOH/ ethylene glycol solution I and H is prepared respectively 3pO 4/ ethylene glycol solution I, obtains suspension a1 after mixing; By MnSO 4mix with the mixed solvent of ethylene glycol/deionized water, obtain solution b1; Again solution b1 is dropwise instilled in solution a1, stir and obtain solution c1;
2) LiOH/ ethylene glycol solution II and H is prepared respectively 3pO 4/ ethylene glycol solution II, obtains suspension a2 after mixing; By FeSO 4mix with ethylene glycol, obtain solution b2; Again solution b2 is dropwise instilled in solution a2, stir and obtain solution c2;
3) solution c2 is dropwise instilled in solution c1, stir and obtain precursor solution, obtain described nano-sheet iron manganese phosphate lithium material through solvent thermal reaction and reprocessing.
4. the preparation method of nano-sheet iron manganese phosphate lithium material according to claim 3, is characterized in that, step 1) in, the molar concentration of described LiOH/ ethylene glycol solution I is 1 ~ 4mol/L, MnSO 4, H 3pO 4be 1:1.1 ~ 1.16:3 with the mol ratio of LiOH.
5. the preparation method of nano-sheet iron manganese phosphate lithium material according to claim 3, is characterized in that, step 1) in, in described mixed solvent, the volume ratio of ethylene glycol and deionized water is 1:1;
Described LiOH/ ethylene glycol solution I, H 3pO 4/ ethylene glycol solution I is 1:1:1 with the volume ratio of solution b1.
6. the preparation method of nano-sheet iron manganese phosphate lithium material according to claim 3, is characterized in that, step 2) in, the molar concentration of described LiOH/ ethylene glycol solution II is 1/9, H of the molar concentration of LiOH/ ethylene glycol solution I 3pO 4the molar concentration of/ethylene glycol solution II is H 3pO 41/9, FeSO in solution b2 of the molar concentration of/ethylene glycol solution I 4molar concentration be MnSO in solution b1 4molar concentration 1/9;
Described LiOH/ ethylene glycol solution II, H 3pO 4the volume ratio of/ethylene glycol solution II and solution b2 is 1:1:1.
7. the preparation method of nano-sheet iron manganese phosphate lithium material according to claim 3, is characterized in that, step 3) in, solution c1 mixes with solution c2 equal-volume.
8. the preparation method of nano-sheet iron manganese phosphate lithium material according to claim 3, is characterized in that, step 3) in, described solvent thermal reaction reacts 6 ~ 9h at 140 ~ 170 DEG C.
9. a nano-sheet iron manganese phosphate lithium material according to claim 1 is in the application be used as or prepare in anode material for lithium-ion batteries.
CN201510163036.6A 2015-04-08 2015-04-08 Nanometer piece shaped LMFP material, and manufacturing method and application thereof Active CN104852046B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510163036.6A CN104852046B (en) 2015-04-08 2015-04-08 Nanometer piece shaped LMFP material, and manufacturing method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510163036.6A CN104852046B (en) 2015-04-08 2015-04-08 Nanometer piece shaped LMFP material, and manufacturing method and application thereof

Publications (2)

Publication Number Publication Date
CN104852046A true CN104852046A (en) 2015-08-19
CN104852046B CN104852046B (en) 2017-01-18

Family

ID=53851516

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510163036.6A Active CN104852046B (en) 2015-04-08 2015-04-08 Nanometer piece shaped LMFP material, and manufacturing method and application thereof

Country Status (1)

Country Link
CN (1) CN104852046B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105552341A (en) * 2016-02-04 2016-05-04 苏州工业园区恒量咨询有限公司 Electrochemical active positive electrode material and preparation method thereof
CN105633366A (en) * 2015-12-30 2016-06-01 镇江宜能新能源材料科技有限公司 C and lithium-vanadium oxide conducting layer-cocoated lithium ferric manganese phosphate cathode material and preparation method thereof
CN105870416A (en) * 2016-04-22 2016-08-17 安徽工业大学 High-rate olivine-type phosphate nanosheet positive electrode material and preparation method thereof
CN106935851A (en) * 2015-12-31 2017-07-07 惠州比亚迪电池有限公司 A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and positive pole and lithium battery
CN108448111A (en) * 2018-01-17 2018-08-24 上海应用技术大学 A kind of preparation method of sheet lithium ion battery positive pole material phosphoric acid cobalt lithium
CN115636402A (en) * 2022-10-28 2023-01-24 深圳市德方纳米科技股份有限公司 Lithium manganese iron phosphate material and preparation method and application thereof
CN115806282A (en) * 2022-11-22 2023-03-17 贵州雅友新材料有限公司 Flaky lithium manganese iron phosphate and synthesis method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103000862A (en) * 2011-09-09 2013-03-27 株式会社半导体能源研究所 Positive electrode for lithium secondary battery, manufacturing method thereof, and lithium secondary battery
CN103337628A (en) * 2013-06-18 2013-10-02 常州大学 Method for synthesizing positive material nano lithium manganese phosphate of lithium ion battery
US20140295275A1 (en) * 2008-04-14 2014-10-02 Dow Global Technologies Llc Lithium manganese phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140295275A1 (en) * 2008-04-14 2014-10-02 Dow Global Technologies Llc Lithium manganese phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries
CN103000862A (en) * 2011-09-09 2013-03-27 株式会社半导体能源研究所 Positive electrode for lithium secondary battery, manufacturing method thereof, and lithium secondary battery
CN103337628A (en) * 2013-06-18 2013-10-02 常州大学 Method for synthesizing positive material nano lithium manganese phosphate of lithium ion battery

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105633366A (en) * 2015-12-30 2016-06-01 镇江宜能新能源材料科技有限公司 C and lithium-vanadium oxide conducting layer-cocoated lithium ferric manganese phosphate cathode material and preparation method thereof
CN106935851A (en) * 2015-12-31 2017-07-07 惠州比亚迪电池有限公司 A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and positive pole and lithium battery
CN106935851B (en) * 2015-12-31 2019-11-29 惠州比亚迪电池有限公司 A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and anode and lithium battery
CN105552341A (en) * 2016-02-04 2016-05-04 苏州工业园区恒量咨询有限公司 Electrochemical active positive electrode material and preparation method thereof
CN105870416A (en) * 2016-04-22 2016-08-17 安徽工业大学 High-rate olivine-type phosphate nanosheet positive electrode material and preparation method thereof
CN105870416B (en) * 2016-04-22 2018-05-18 安徽工业大学 A kind of high magnification phosphate of olivine type nano flake positive electrode and preparation method thereof
CN108448111A (en) * 2018-01-17 2018-08-24 上海应用技术大学 A kind of preparation method of sheet lithium ion battery positive pole material phosphoric acid cobalt lithium
CN115636402A (en) * 2022-10-28 2023-01-24 深圳市德方纳米科技股份有限公司 Lithium manganese iron phosphate material and preparation method and application thereof
CN115636402B (en) * 2022-10-28 2024-04-16 深圳市德方纳米科技股份有限公司 Lithium iron manganese phosphate material and preparation method and application thereof
CN115806282A (en) * 2022-11-22 2023-03-17 贵州雅友新材料有限公司 Flaky lithium manganese iron phosphate and synthesis method and application thereof
CN115806282B (en) * 2022-11-22 2024-05-10 贵州雅友新材料有限公司 Flaky lithium iron manganese phosphate and synthesis method and application thereof

Also Published As

Publication number Publication date
CN104852046B (en) 2017-01-18

Similar Documents

Publication Publication Date Title
Peng et al. Self-assembled LiNi1/3Co1/3Mn1/3O2 nanosheet cathodes with tunable rate capability
Zhang et al. Li4Ti5O12 prepared by a modified citric acid sol–gel method for lithium-ion battery
Lu et al. Enhancement of F-doping on the electrochemical behavior of carbon-coated LiFePO4 nanoparticles prepared by hydrothermal route
CN102738458B (en) Surface modification method of lithium-rich cathode material
CN104852046B (en) Nanometer piece shaped LMFP material, and manufacturing method and application thereof
Xu et al. The preparation and role of Li2ZrO3 surface coating LiNi0. 5Co0. 2Mn0. 3O2 as cathode for lithium-ion batteries
CN104241626B (en) The process for preparing sol-gel of lithium ion battery lithium vanadate negative material
Zhang et al. Hierarchical architectured MnCO 3 microdumbbells: facile synthesis and enhanced performance for lithium ion batteries
Yang et al. Cation disordered rock salt phase Li 2 CoTiO 4 as a potential cathode material for Li-ion batteries
EP2784853B1 (en) Lithium transistion metal titanate with a spinel structure, method for its manufacturing, its use, Li-ion cell and battery
JP2016524311A (en) Method for producing lithium ion battery positive electrode material
Yang et al. Sol–gel-assisted, fast and low-temperature synthesis of La-doped Li 3 V 2 (PO 4) 3/C cathode materials for lithium-ion batteries
Wang et al. Polymer-chelation synthesis of compositionally homogeneous LiNi1/3Co1/3Mn1/3O2 crystals for lithium-ion cathode
CN103413944A (en) Lithium manganese phosphate positive electrode material and preparation method thereof
Mao et al. Nanoparticle-assembled LiMn2O4 hollow microspheres as high-performance lithium-ion battery cathode
Zhao et al. Environmentally benign and scalable synthesis of LiFePO4 nanoplates with high capacity and excellent rate cycling performance for lithium ion batteries
Ram et al. Synthesis and improved electrochemical performance of LiMn2–xGdxO4 based cathodes
CN114335534A (en) Lithium cobaltate positive electrode material coated and modified by zirconium lithium phosphate fast ion conductor and preparation method and application thereof
CN107180965B (en) A kind of nano-scale lithium iron phosphate/graphene composite material and its preparation method and application
CN105006569B (en) Nanoscale lithium manganese phosphate material and its preparation method and application
Wang et al. Nano-sized over-lithiated oxide by a mechano-chemical activation-assisted microwave technique as cathode material for lithium ion batteries and its electrochemical performance
Jiang et al. One-pot hydrothermal synthesis of LiMn 2 O 4 cathode material with excellent high-rate and cycling properties
CN114203993B (en) Li (lithium ion battery) 2 SeO 4 Fast ion conductor modified lithium ion battery anode material
He et al. Wet chemical synthesis of tin oxide-based material for lithium ion battery anodes
Pei et al. Porous materials for lithium-ion batteries

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant