CN101605722A - Crystalline nanometer LiFeMPO 4Synthetic - Google Patents

Crystalline nanometer LiFeMPO 4Synthetic Download PDF

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CN101605722A
CN101605722A CNA2007800476177A CN200780047617A CN101605722A CN 101605722 A CN101605722 A CN 101605722A CN A2007800476177 A CNA2007800476177 A CN A2007800476177A CN 200780047617 A CN200780047617 A CN 200780047617A CN 101605722 A CN101605722 A CN 101605722A
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life
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斯特凡·勒瓦瑟
米谢勒·万图尔努
皮埃尔·吉博
克里斯蒂安·马斯克利耶
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Umicore NV SA
Centre National de la Recherche Scientifique CNRS
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Centre National de la Recherche Scientifique CNRS
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    • 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
    • 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
    • C01B25/30—Alkali metal phosphates
    • 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
    • C01B25/37—Phosphates of heavy metals
    • 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
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • 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
    • C01B25/37—Phosphates of heavy metals
    • C01B25/377—Phosphates of heavy metals of manganese
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to lithium secondary battery, and relate more specifically in non-aqueous electrochemical cells with respect to Li +The anode material that/Li operates down greater than the electromotive force of 2.8V.Especially, the present invention relates to crystalline nanometer olivine-type LiFe 1-xM xPO 4Powder, wherein M is Co and/or Mn and 0＜x＜1, it has little particle diameter and narrow size distribution.The present invention has also described direct precipitation method, and it comprises the steps: to provide pH is 6 to 10 water-based mixture, and this mixture contains dipolar aprotic additive and as the Li of precursor component (I), Fe (II), P (V)And Co (II)And/or Mn (II)Described water-based mixture is heated to the temperature of being less than or equal to its boiling point under barometric point, thereby with crystalline LiFe 1-xM xPO 4Powder precipitation.Having obtained superfine particle diameter, is 275nm for Mn for about 80nm with for Co, and the two all has narrow distribution.This thin particle diameter it is believed that and caused excellent height electric leakage performance, the needs for conductivity additive are minimized.This narrow distribution makes that electrode production is easier and has guaranteed uniform distribution of current in described battery.

Description

Crystalline nanometer LiFeMPO 4Synthetic
Technical field
The present invention relates to crystalline nanometer LiFe 1-xM xPO 4(LFMP) powder, it has little particle diameter and narrow size distribution, and it is used as positive electrode material in the Li battery.Also described preferred production methods, it is undertaken by make described crystalline nanometer powder precipitation under low temperature and barometric point.
Background technology
Since people's such as initial Padhi work (JES, 144 (1997), 1188), phosphoric acid salt peridotites (phospho-olivines) LiMPO 4(wherein M=Fe, Ni, Co, Mn ...) to have demonstrated be to wait to be used as the potential alternative material of Li battery with cathode material.In the composition of all these isomorphism types, LiFePO 4The commercialization that is studied maximum and its realization at present is owing to the very high performance (international open WO2004/001881A2) about reversible capacity, speed ability (rate properties) and cycle life aspect.
LiCoPO 4(people such as Amine, ESSL, 3, (2000), 178) and LiMnPO 4(97-98 (2001) 430 for people such as Okada, J.Power Sources), because their higher redox-potential values are 4.8V and 4.1V with respect to Li respectively usually, they are to make us interested especially, because and LiFePO 4(with respect to Li is 3.5V, people such as Chen, JES, 149 (2002) A1184) compares them provides higher energy density.
Yet, be well known that now these phosphoric acid salt peridotites materials have poor electroconductibility and lead ionic people such as (, JES, 152 (2005) A913) Delacourt, it is necessary therefore needing the microstructure of these compounds of optimization.People such as Striebel (JES, 152, (2005), A664) obtain to improve even claim matrix conductivity by conductive coating, the researchist of exploitation battery also wishes to exist the compound of following the unknown up to now, and it has the primary particle diameter of 50 to 100nm scopes, and generally speaking, should attempt size distribution is minimized, thereby produce better energy efficient.
About blended metal phosphate, for example LiFe 1-xMn xPO 4Material, optimized result is at C/LiFe 0.4Mn 0.6PO 4Obtain on the matrix material, wherein C plays the effect of sintering inhibitor.This method causes forming blended C/LiFeMnPO 4Matrix material, the scope of its particle are 100 to 200nm (people such as Mi, Mater.Sci.Eng., 129 (2006) 8).Similarly the result by people such as Lloris (ESSL, 5 (2002) A234) at pure LiCoPO 4Last acquisition, it has the little particle of 200 to 300nm scopes.Up to the present, also not open about LiFe 1-xCo xPO 4The data of material.
Except little particle diameter, also must emphasize size distribution is narrowed down, guaranteeing on electrode distribution of current uniformly, and therefore obtain better battery performance, particularly high energy efficiency and long cycle life.Therefore, the object of the present invention is to provide crystalline LFMP powder, it has little particle diameter and narrow size distribution.
Summary of the invention
In order to achieve the above object, the invention discloses the method that produces metal phosphate powders, described phosphate powder provides with respect to above-mentioned materials improvement in essence.
The LiFe that is used for synthetic crystallization of the present invention 1-xMn xPO 4The method of powder, wherein M is one or both among Co and the Mn, and 0＜x＜1, preferred 0.4＜x＜0.95, this method comprises the steps:
-pH is provided is 6 to 10 water-based mixture, this mixture contains dipolar aprotic additive and as the Li of precursor component (I), Fe (II), P (V)And Co (II)And Mn (II)In one or both;
-described water-based mixture is heated to the temperature of being less than or equal to its boiling point under barometric point, thereby with crystalline LiFe 1-xM xPO 4Powder precipitation.The powder that is obtained can experience by it is heated the aftertreatment of carrying out in non-oxidizable condition.
Yet pH is 6 to 8 to be preferred, thereby has avoided Li 3PO 4Any precipitation.Described additive is dipolar aprotic compound preferably, and it does not have chelating or complexation propensity.The Heating temperature of preferred described water-based mixture is at least 60 ℃.
Crystalline LiFe 1-xM xPO 4The production of powder or hot aftertreatment can be advantageously carried out in the presence of at least a other component, and described other component is carbonaceous material or electronic conduction material particularly, perhaps the precursor of electronic conduction material.
Usefully with Li (I)At least a portion introduce as LiOH.Similarly, at least a portion P (V)Can be used as H 3PO 4Introduce.The pH of described water-based mixture can be by regulating LiOH and H 3PO 4Ratio and obtain.
Suggestion use boiling point under barometric point is 100 to 150 ℃, preferred 100 to 120 ℃ water-based mixture.Methyl-sulphoxide (DMSO) is preferably used as described dipolar aprotic additive.Described water-based mixture advantageously contains 5 to 50mol% and preferred 10 to 30mol% DMSO.Lower DMSO concentration causes thicker size distribution; Higher concentration limit the applicability of water, force the volume of increase equipment.
Aftertreatment LiFe 1-xM xPO 4Step advantageously carry out being up under the temperature of 675 ℃ and preferred at least 300 ℃.Selecting lower limit is in order to increase sedimentary LiFe 1-xM xPO 4Crystallinity; Selecting the upper limit is for fear of described LiFe 1-xM xPO 4Resolve into phosphatization manganese.
Described electronic conduction material can be a carbon, particularly Dao Dian carbon or carbon fiber.Perhaps, can use the precursor of electronic conduction material, particularly polymkeric substance or sugared type macromole.
The invention still further relates to crystalline LiFe 1-xMn xPO 4Powder, 0＜x＜1 wherein, preferred 0.4＜x＜0.95, it is used as electrode materials in battery, and it has following size distribution, and wherein median size d50 is for less than 100nm be preferably greater than 30nm.Maximum particle diameter preferably is less than or equal to 500nm.Described size distribution is single mode preferably, and ratio (d90-d10)/d50 is advantageously less than 1.5, preferably less than 1.3.
Another embodiment of the invention relates to composite powder, and it contains above-mentioned crystalline LiMnPO 4Powder and the conductivity additive that is up to 10 weight %.Other embodiments relate to the electrode mix (electrode mix) that can adopt this composite powder preparation.The carbon, carbon fiber of conduction, be suitable for especially well by the decolorizing carbon that the organic carbonaceous material decomposition is obtained, electronic conductive polymer, metal-powder and steel fiber and make conductivity additive.
Another embodiment of the invention relates to described composite powder by described powder is mixed the purposes that is used to make embedding lithium type electrode with the additive of the carbon that has conduction.
The invention still further relates to crystalline LiFe 1-xCo xPO 4Powder, 0＜x＜1 wherein, preferred 0.4＜x＜0.95, it is used as electrode materials in battery, and it has following size distribution, and wherein median size d50 is for less than 300nm be preferably greater than 30nm.Maximum particle diameter preferably is less than or equal to 900nm.Described size distribution is single mode preferably, and ratio (d90-d10)/d50 is advantageously less than 1.5, preferably less than 1.1.
Another embodiment of the invention relates to composite powder, and it contains above-mentioned crystalline LiFe 1-xCo xPO 4Powder and the conductivity additive that is up to 10 weight %.Other embodiments relate to the electrode mix that can adopt this composite powder preparation.The carbon, carbon fiber of conduction, be suitable for especially well by the decolorizing carbon that the organic carbonaceous material decomposition is obtained, electronic conductive polymer, metal-powder and steel fiber and make conductivity additive.
Another embodiment of the invention relates to the purposes that by described composite powder is mixed with the additive of the carbon that has conduction described composite powder is used to make embedding lithium type electrode.
Compared with prior art, this product has listed for considering in lithium cell as needed all advantages of potential cathode material:
-the direct precipitation of crystalline LFMP prevents any grain growing relevant with sintering process at low temperatures.Obtain nanometer particle size.This has reduced kinetic limitation, because the Li ion transmits in described particle, thereby has strengthened the fast charge/discharge performance of battery.
-described narrow size distribution has been guaranteed uniform distribution of current in described battery.This is a particularly important on high charge/discharge rates, and the particle consumption that wherein thinner particle is thicker is more, the phenomenon that causes particle finally to degenerate and cause cell container to fail in use.In addition, it makes that the described electrode of manufacturing is easier.
The boiling point suggestion of described water-based mixture under barometric point is 100 to 150 ℃, preferred 100 to 120 ℃.Use and the mixable additive of water are as cosolvent, and described cosolvent precipitates into nuclear dynamics with increase, have therefore reduced LiMnPO 4The size of nano particle.Except can be with water miscible, useful cosolvent should be non-proton, promptly only shows little or does not have the division of following hydrogen ion to discharge fully.The cosolvent that shows coordination or chelating character, ethylene glycol does not for example demonstrate and is fit to, because they can reduce LiMnPO 4Sedimentary kinetics, and therefore cause bigger particle diameter.Suitable dipolar aprotic solvent Shi diox, tetrahydrofuran (THF), N-(C 1-C 18-alkyl) pyrrolidone, ethylene glycol dimethyl ether, aliphatics C 1-C 6The C of carboxylic acid 1-C 4Alkyl ester, C 1-C 6Dialkyl ether, aliphatics C 1-C 4The N of carboxylic acid, N-two (C 1-C 4-alkyl) acid amides, tetramethylene sulfone, 1,3-two (C 1-C 8-alkyl)-2-imidazolinedione, N-(C 1-C 8-alkyl) hexanolactam, N, N, N ', N '-four (C 1-C 8-alkyl) urea, 1,3-two (C 1-C 8-alkyl)-3,4,5,6-tetrahydrochysene-2 (1H)-pyrimidone, N, N, N ', N '-four (C 1-C 8-alkyl) sulphonamide, 4-formyl morpholine, 1-formyl piperidine or 1-carbonyl pyrrolidine, N-(C 1-C 18-alkyl) pyrrolidone, N-Methyl pyrrolidone (NMP), N-octylpyrrolidone, N-dodecyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide or hexamethylphosphoramide.Other alternative material, for example tetraalkyl ureas also is fine.Can also use the mixture of above-mentioned dipolar aprotic solvent.In preferred embodiments, methyl-sulphoxide (DMSO) is used as solvent.
Description of drawings
Exemplary illustration description of drawings of the present invention is as follows.
Fig. 1: LiFe after the reaction times of 18h 0.5Mn 0.5PO 4Sedimentary XRD.
Fig. 2: described LiFe 0.5Mn 0.5PO 4The SEM picture.
Fig. 3: described LiFe 0.5Mn 0.5PO 4Volumetric particle size distribution and cumulative distribution (% is to nm).
Fig. 4: LiFe after the reaction times of 18h 0.5Co 0.5PO 4Sedimentary XRD.
Fig. 5: described LiFe 0.5Co 0.5PO 4The SEM picture.
Fig. 6: described LiFe 0.5Co 0.5PO 4Volumetric particle size distribution and cumulative distribution (% is to nm).
Embodiment
Further exemplary illustration the present invention among the embodiment hereinafter.
Embodiment 1:LiFe 0.5Mn 0.5PO 4Synthetic
In the first step, under agitation DMSO is joined as in the inferior molar solution, the described molar solution that waits is for being dissolved in H 20.05M among the O at MnNO 34H 2Mn among the O (II), 0.05M at FeSO 47H 2Fe among the O (II)With 0.1M at H 3PO 4In P (V)Wait molar solution.The amount of regulating DMSO is with the complete combination thing of the DMSO of the water that obtains 50 volume % and 50 volume %, and the DMSO of the water of described 50 volume % and 50 volume % corresponds respectively to about 80 moles of % and 20 moles of %.
In second step, with the LiOHH of 0.3M 2The O aqueous solution joins in the described solution under 25 ℃; The pH value is increased to 6.5 to 7.5 thus.Final Li: Fe: Mn: the P ratio approached 3: 0.5: 0.5: 1.
In the 3rd step, the temperature of described solution is elevated to the boiling point that is up to solvent, it is 108 to 110 ℃.Behind the 18h, with sedimentation and filtration and the water thorough washing that obtains.The pure crystalline LiFe that is obtained 0.5Mn 0.5PO 4Be shown among Fig. 1.
Accurate unit cell parameters is a=10.390
Figure G2007800476177D00061
, b=6.043
Figure G2007800476177D00062
C=4.721
Figure G2007800476177D00063
, wherein unit cell volume is 296.4
Figure G2007800476177D00064
This and Vegard law coincide well, described Vegard law explanation be that under the situation of sosoloid, the unit cell volume of mix products should be at the unit cell volume of final product (for pure LiFePO 4Be 291
Figure G2007800476177D00065
, for pure LiMnPO 4Be 302
Figure G2007800476177D00066
) between.
The picture of Fig. 2 has shown the monodispersed little crystalline particle of 50～100nm scope.The volumetric particle size distribution of described product adopts image analysis to measure.As shown in Figure 3, the d50 value is about 80nm, and the relative span that is defined as (d90-d10)/d50 be about 1.2 (d10=45nm, d90=145nm).
Embodiment 2:LiFe 0.5Co 0.5PO 4Synthetic
In the first step, under agitation DMSO is joined as in the inferior molar solution, the described molar solution that waits is for being dissolved in H 20.05M among the O at MnSO 4H 2Mn among the O (II), 0.05M at CoNO 36H 2Co among the O (II)H with 0.1M 3PO 4In P (V)Wait molar solution.The amount of regulating DMSO is with the complete combination thing of the DMSO of the water that obtains 50 volume % and 50 volume %.
In second step, with the LiOHH of 0.3M 2The aqueous solution of O joins in the described solution under 25 ℃; The pH value is increased to 6.5 to 7.5 thus.Final Li: Fe: Co: the P ratio approached 3: 0.5: 0.5: 1.
In the 3rd step, the temperature of described solution is elevated to the boiling point that is up to solvent, it is 108 to 110 ℃.Behind the 18h, with sedimentation and filtration and the water thorough washing that obtains.The pure crystalline LiFe that is obtained 0.5Co 0.5PO 4Be shown among Fig. 4.
Accurate unit cell parameters is a=10.292
Figure G2007800476177D00071
, b=5.947 C=4.712
Figure G2007800476177D00073
, wherein unit cell volume is 288.4
Figure G2007800476177D00074
This coincide well with the Vegard law once more, described Vegard law explanation be that under the situation of sosoloid, the unit cell volume of mix products should be at the unit cell volume of final product (for pure LiFePO 4Be 291
Figure G2007800476177D00075
, for pure LiCoPO 4Be 284
Figure G2007800476177D00076
) between.
The picture of Fig. 5 has shown the monodispersed little crystalline particle of 200～300nm scope.The volumetric particle size distribution of described product adopts image analysis to measure.As shown in Figure 6, the d50 value is about 275nm, and the relative span that is defined as (d90-d10)/d50 be about 1.0 (d10=170nm, d90=450nm).

Claims (23)

1. prepare crystalline LiFe 1-xM xPO 4The method of powder, wherein M is one or both and 0＜x＜1 among Co and the Mn, this method comprises the steps:
-pH is provided is 6 to 10 water-based mixture, this mixture contains dipolar aprotic additive and as the Li of precursor component (I), Fe (II), P (V)And Co (II)And Mn (II)In one or both;
-described water-based mixture is heated to the temperature of being less than or equal to its boiling point under barometric point, thereby with crystalline LiFe 1-xM xPO 4Powder precipitation.
2. method according to claim 1 is carried out aftertreatment LiFe subsequently 1-xM xPO 4The step of powder, described aftertreatment are by with LiFe 1-xM xPO 4Powder heats under non-oxidizable condition and carries out.
3. according to claim 1 and 2 described methods, it is characterized in that described crystalline LiFe 1-xM xPO 4The manufacturing of powder or by being to carry out in the presence of at least a other component in the aftertreatment carried out of heating under the non-oxidizable condition, described other component be the precursor of carbonaceous material or electronic conduction material or electronic conduction material particularly.
4. method according to claim 1 is wherein to the Li of small part (I)Introduce as LiOH.
5. method according to claim 1 is wherein to the P of small part (V)Be as H 3PO 4Introduce.
6. according to claim 4 and 5 described methods, the pH of wherein said water-based mixture is by regulating LiOH and H 3PO 4Ratio obtain.
7. according to each described method in the claim 1 to 6, it is characterized in that the boiling point of described water-based mixture under barometric point is 100 to 150 ℃, and be preferably 100 to 120 ℃.
8. according to each described method in the claim 1 to 7, it is characterized in that the non-proton dipole additive that is included in the described water-based mixture is a methyl-sulphoxide.
9. according to each described method in the claim 2 to 8, it is characterized in that LiFe 1-xM xPO 4Post-processing step be to carry out being up under the temperature of 675 ℃ and preferred at least 300 ℃.
10. according to each described method in the claim 3 to 9, it is characterized in that described electronic conduction material is a carbon, particularly Dao Dian carbon or carbon fiber.
11., it is characterized in that the precursor of described electronic conduction material is carbonaceous conductive material, particularly polymkeric substance or sugared type macromole according to each described method in the claim 3 to 9.
12. crystalline LiFe 1-xMn xPO 4Powder, 0＜x＜1 wherein, it is used as electrode materials in battery, and it has following size distribution, and wherein median size d50 is for less than 100nm be preferably greater than 30nm.
13. LiFe according to claim 12 1-xMn xPO 4Powder is characterized in that, described maximum particle diameter is less than or equal to 500nm.
14. according to claim 12 or 13 described LiFe 1-xMn xPO 4Powder is characterized in that, described size distribution is a single mode, and ratio (d90-d10)/d50 is less than 1.5, preferably less than 1.3.
15. composite powder, it contains each described LiFe in the with good grounds claim 12 to 14 1-xMn xPO 4Powder, and the conductivity additive that is up to 10 weight %.
16. contain the electrode mix of composite powder according to claim 15.
17. composite powder according to claim 15 is by mixing the purposes that is used to make embedding lithium type electrode with described powder with the additive of the carbon that has conduction.
18. crystalline LiFe 1-xCo xPO 4Powder, 0＜x＜1 wherein, it is used as electrode materials in battery, and it has following size distribution, and wherein median size d50 is for less than 300nm be preferably greater than 30nm.
19. LiFe according to claim 18 1-xCo xPO 4Powder is characterized in that, described maximum particle diameter is less than or equal to 900nm.
20. according to claim 18 or 19 described LiFe 1-xCo xPO 4Powder is characterized in that, described size distribution is a single mode, and ratio (d90-d10)/d50 is less than 1.5, preferably less than 1.1.
21. composite powder, it contains each described LiFe in the with good grounds claim 18 to 20 1-xMn xPO 4Powder, and the conductivity additive that is up to 10 weight %.
22. contain the electrode mix of composite powder according to claim 21.
23. composite powder according to claim 21 is by mixing the purposes that is used to prepare embedding lithium type electrode with described powder with the additive of the carbon that has conduction.
CNA2007800476177A 2006-12-22 2007-11-19 Crystalline nanometer LiFeMPO 4Synthetic Pending CN101605722A (en)

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CN102781827A (en) * 2010-03-19 2012-11-14 户田工业株式会社 Method for producing lithium manganese iron phosphate particulate powder, lithium manganese iron phosphate particulate powder and non-aqueous electrolyte secondary battery using that particulate powder
CN102947219A (en) * 2010-01-28 2013-02-27 南方化学知识产权有限两合公司 Substituted lithium-manganese metal phosphate
CN104752720A (en) * 2013-12-30 2015-07-01 比亚迪股份有限公司 Lithium manganese ferric phosphate, preparation method and application thereof
US9109286B2 (en) 2010-06-18 2015-08-18 Semiconductor Energy Laboratory Co., Ltd. Method of manufacturing power storage device
CN107697899A (en) * 2017-10-31 2018-02-16 中钢集团安徽天源科技股份有限公司 Preparation method, lithium ferric manganese phosphate, cell positive material and the secondary cell of battery-grade iron phosphate manganese

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