CN101355162B - Method for manufacturing lithium-iron-phosphorus compound oxide carbon complex and method for manufacturing coprecipitate containing lithium, iron, and phosphorus - Google Patents
Method for manufacturing lithium-iron-phosphorus compound oxide carbon complex and method for manufacturing coprecipitate containing lithium, iron, and phosphorus Download PDFInfo
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- CN101355162B CN101355162B CN2008101442140A CN200810144214A CN101355162B CN 101355162 B CN101355162 B CN 101355162B CN 2008101442140 A CN2008101442140 A CN 2008101442140A CN 200810144214 A CN200810144214 A CN 200810144214A CN 101355162 B CN101355162 B CN 101355162B
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- C—CHEMISTRY; METALLURGY
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
An object of the present invention to provide a method for manufacturing a lithium-iron-phosphorus compound oxide carbon complex suitable for adjusting the composition of Li, Fe, and P of a lithium-iron-phosphorus compound oxide in the lithium-iron-phosphorus compound oxide carbon complex easily, obtaining a single phase of LiFePO4 on an X-ray diffraction analysis basis, and imparting excellent battery performance to a lithium secondary battery. The method for manufacturing a lithium-iron-phosphorus compound oxide carbon complex includes the steps of allowing a solution containing lithium ions, divalent iron ions, and phosphate ions (Solution A) to contact with a solution containing an alkali (Solution B) while pH is controlled at 5.5 to 9.5 so as to produce a coprecipitate containing lithium, iron, and phosphorus in a first step, mixing the coprecipitate and an electrically conductive carbon material so as to produce a raw material mixture for calcining in a second step, and calcining the raw material mixture for calcining in an inert gas atmosphere so as to produce the lithium-iron-phosphorus compound oxide carbon complex in a third step.
Description
Technical field
The present invention relates to manufacturing approach as the useful Phosphorus compound oxide carbon complex of lithium iron of cathode active material for lithium secondary battery.
Background technology
In recent years, along with developing rapidly of removableization, wireless penetration in the household electrical appliance, as the power supply of miniature electric machines such as portable computer, portable phone, video camera, lithium rechargeable battery obtains practicability.For this lithium rechargeable battery; Delivered report (" マ テ リ ア Le リ サ one チ Block レ テ イ Application " (" investigation of materials ") vol15 that cobalt acid lithium can be effective as the positive active material of lithium rechargeable battery from 1980 by water island etc.; P783-789 (1980)) since; Research and development about cobalt acid lithium make progress energetically, have formed many motions so far.
But, because Co on earth skewness, be rare resource, so, for example carrying out LiNiO as the new positive active material that replaces cobalt acid lithium
2, LiMn
2O
4, LiFeO
2, LiFePO
4Deng exploitation.
LiFePO
4Bulk density big, be 3.6g/cm
3, producing the high potential of 3.4V, theoretical capacity is also up to 170mAh/g, and, LiFePO
4Under initial condition per 1 Fe atom contain 1 can be on electrochemistry the Li of dedoping, so, as expecting much of the positive active material of the new lithium secondary battery that replaces cobalt acid lithium.
As this LiFePO
4Manufacturing approach, the method that obtains with solid phase method has been proposed, but in order to obtain LiFePO single-phase in the X-ray diffraction analysis
4, need obtain the accurate homogeneous mixture that mixes of each raw material, be difficult in industry, obtain the material of stay in grade.
In addition, as the method for the homogeneous mixture that easily obtains each raw material, the various schemes of coprecipitation have been proposed to use.For example, in following patent documentation 1, proposed to use the method for in the solution that contains lithium dihydrogen phosphate, ferric sulfate, adding the co-precipitation body that contains the solution of lithium hydroxide and obtain.And, in following patent documentation 2, proposed to use in the solution of the compound that contains the phosphate anion that in solution, dissociates and metallic iron interpolation lithium carbonate or lithium hydroxide and the method for the co-precipitation body that obtains.In addition, in the following patent documentation 3, proposed to use mixed ammonium/alkali solutions in the phosphate aqueous solution that contains lithium salts, molysite and water-soluble reducing agent and the method for the compound phosphoric acid thing co-precipitation body of the lithium that obtains and iron.
Patent documentation 1: Japanese Patent Laid table 2004-525059 communique, the 5th page
Patent documentation 2: International Publication WO2004/036671 brochure, the 1st page
Patent documentation 3: Japanese Patent Laid is opened 2002-117831 communique, the 1st page
But, in the method for using these coprecipitations, the composition of Li, Fe and P adjustment difficulty, and, exist to be difficult to obtain LiFePO single-phase in the X-ray diffraction analysis
4Problem.
Summary of the invention
Therefore; The objective of the invention is to; The manufacturing approach of the Phosphorus compound oxide carbon complex of a kind of lithium iron is provided, and the composition adjustment of Li, Fe and the P of the Phosphorus composite oxides of lithium iron in the Phosphorus compound oxide carbon complex of this lithium iron can access LiFePO single-phase in the X-ray diffraction analysis easily
4, can give lithium secondary battery with excellent battery performance.
The inventor etc. further investigate based on above-mentioned actual conditions repeatedly; The result finds; The solution (A liquid) that will contain lithium ion, divalent iron ion and phosphate anion with contain aqueous slkali (B liquid) and be controlled in the pH of particular range, and makes it contact and react, thereby the composition adjustment that contains Li, Fe and P in the co-precipitation body of lithium iron phosphorus becomes easy; The ratio of components that can make Li, Fe and P was near 1: 1: 1; So the adjustment of the composition of Li, Fe and P in the Phosphorus compound oxide carbon complex of lithium iron becomes easily, and, can obtain the co-precipitation body with high yield.In addition, through in the inertness atmosphere, firing the co-precipitation body that so obtains and the mixture of conductive carbon material, can access and be seen as LiFePO from X-ray diffraction analysis
4Single-phase Phosphorus composite oxide particle of lithium iron and the Phosphorus compound oxide carbon complex of the homodisperse lithium iron of conductive carbon material.And the Phosphorus compound oxide carbon complex of finding so to obtain of lithium iron has so far been accomplished the present invention as the battery performance that the lithium secondary battery of positive active material has excellence.
Promptly; The present invention (1) provides the manufacturing approach of the Phosphorus compound oxide carbon complex of a kind of lithium iron; It is characterized in that, comprising: first operation is controlled at 5.5～9.5 with pH; And the solution (A liquid) that contains lithium ion, divalent iron ion and phosphate anion is contacted with containing aqueous slkali (B liquid), obtain containing the co-precipitation body of lithium, iron and phosphorus; Second operation is mixed this co-precipitation body and conductive carbon material, obtains firing raw mix; With the 3rd operation, in the inertness atmosphere, this is fired raw mix fire, obtain the Phosphorus compound oxide carbon complex of lithium iron.
The invention effect
According to the present invention; The manufacturing approach of the Phosphorus compound oxide carbon complex of a kind of lithium iron can be provided; The composition adjustment of Li, Fe and the P of the Phosphorus composite oxides of lithium iron in the Phosphorus compound oxide carbon complex of this lithium iron easily; The ratio of components that can make Li, Fe and P can access LiFePO single-phase in the X-ray diffraction near 1: 1: 1
4, can give lithium secondary battery with excellent battery performance.
Description of drawings
Fig. 1 is the X-ray diffractogram of the Phosphorus compound oxide carbon complex of lithium iron that in embodiment 1, obtains.
Fig. 2 is the X-ray diffractogram of the Phosphorus compound oxide carbon complex of lithium iron that in comparative example 1, obtains.
Embodiment
The manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron of the present invention; Comprise: first operation; PH is controlled at 5.5～9.5, and the solution (A liquid) that contains lithium ion, divalent iron ion and phosphate anion is contacted with containing aqueous slkali (B liquid), obtain containing the co-precipitation body of lithium, iron and phosphorus; Second operation is mixed this co-precipitation body and conductive carbon material, obtains firing raw mix; With the 3rd operation, in the inertness atmosphere, this is fired raw mix fire, obtain the Phosphorus compound oxide carbon complex of lithium iron.
First operation of the manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron of the present invention; PH is controlled at 5.5～9.5; And make the solution (A liquid) that contains lithium ion, divalent iron ion and phosphate anion contact and react with containing aqueous slkali (B liquid), obtain containing the co-precipitation body (being designated hereinafter simply as " co-precipitation body ") of lithium, iron and phosphorus thus.
The A liquid of first operation is the aqueous solution that contains lithium ion, divalent iron ion and phosphate anion.
As the lithium source of A liquid, get final product so long as have lithium ion and water-soluble compound, do not limit especially; For example; Can enumerate out lithium sulfate, lithium nitrate, lithium chloride, lithium acetate, lithium carbonate, lithium hydroxide, lithium oxalate etc., wherein, lithium sulfate is low and preferred with price.The lithium source of these A liquid can be used a kind, also can be also with more than 2 kinds.
Divalent source of iron as A liquid; Get final product so long as have divalent iron ion and water-soluble compound; Not special restriction for example, can be enumerated out ferrous sulfate (II), ferric acetate (II), ferric oxalate (II), frerrous chloride (II), ferrous nitrate (II) etc.; Wherein, ferrous sulfate is low and preferred with price.The divalent source of iron of these A liquid can be used a kind, also can be also with more than 2 kinds.
As the source of phosphoric acid of A liquid, get final product so long as have phosphate anion and water-soluble compound, do not limit especially, for example, can not enumerate out phosphoric acid, ammonium dihydrogen phosphate, dibastic sodium phosphate, metaphosphoric acid etc., wherein, phosphoric acid is low and preferred with price.The source of phosphoric acid of these A liquid can be used a kind, also can be also with more than 2 kinds.Wherein, in the present invention, the phosphate anion of so-called A liquid is the general name of phosphate anions such as positive phosphorus acid ion, metaphosphate ion, pyrophosphate ion, triphosphate ion, four phosphate anions.
The ratio of the lithium ion in the A liquid, divalent iron ion and phosphate anion, from the mol ratio of each element of co-precipitation body near Li: Fe: PO
4=1: 1: 1 viewpoint is set out, (the Li: Fe: P) be preferably 0.8～1.2: 0.8～1.2: 1, be preferably 0.95～1.05: 0.95～1.05 especially: 1 of the mol ratio when being scaled lithium atom, divalent iron atom and phosphorus atoms.In addition, the lithium ion content in the A liquid, being scaled the Li atom is 0.1～1.0 mole/L, is preferably 0.5～1.0 mole/L; The divalent iron ion content, being scaled the divalent iron atom is 0.1～1.0 mole/L, is preferably 0.5～1.0 mole/L; It is 0.1～1.0 mole/L that phosphate anion content is scaled phosphorus atoms, is preferably 0.5～1.0 mole/L.Ratio and lithium ion content, divalent iron ion content and phosphate anion content through making lithium ion, divalent iron ion and phosphate anion in the A liquid are in the above-mentioned scope; When modulation A liquid; Because lithium source, divalent source of iron and source of phosphoric acid can not become slow to the dissolution velocity of solution, so industrial efficiency is good; And it is can reduce waste liquid, thereby preferred.
The divalent source of iron of the lithium source of A liquid through making A liquid, A liquid and the source of phosphoric acid of A liquid are dissolved in the water modulates.
The pH of A liquid is preferably below 2.5, is preferably 0.1～1.5 especially.Be in the above-mentioned scope through the pH that makes A liquid, can make the composition adjustment of Li, Fe and P in the co-precipitation body become easy.On the other hand, if the pH of A liquid is higher than above-mentioned scope, then cause being difficult to carry out the composition adjustment of Li, Fe and P in the co-precipitation body easily.
The B liquid of first operation is the aqueous solution that contains alkali, adjusts through alkali source is dissolved in the water.Alkali source as B liquid; Can enumerate out lithium hydroxide, ammonia, NaOH, potassium hydroxide, sodium acid carbonate, saleratus, sodium carbonate, potash etc.; Wherein, preferred NaOH or lithium hydroxide are because be that the lithium of identical element constitutes by the element that constitutes with the Phosphorus compound oxide carbon complex of lithium iron; From the viewpoint that metal impurities reduce, preferred especially lithium hydroxide.The lithium source of these B liquid can be used a kind, also can be also with more than 2 kinds.
The content of the alkali in the B liquid is 0.1～10 equivalent/L, is preferably 1～10 equivalent/L.Through the alkali content in the B liquid is in the above-mentioned scope, can reduce waste liquid.
In first operation, with pH be controlled at 5.5～9.5, preferred 5.5～8.5, carry out contacting of A liquid and B liquid simultaneously.Carry out contacting of A liquid and B liquid in the above-mentioned scope simultaneously through being controlled at, the composition adjustment of the Li in the co-precipitation body, Fe and P becomes easily, and the yield of co-precipitation body improves.On the other hand, if the pH when A liquid contacts with B liquid is lower than above-mentioned scope, because the lithium composition is difficult to separate out, so the ratio of components of the elemental lithium in the co-precipitation body reduces, perhaps lithium, iron or P elements remain in the reaction solution, and yield reduces; In addition, if be higher than above-mentioned scope, the ferro element in the co-precipitation body that then produces is oxidized easily.
The ratio of the amount of the A liquid when A liquid is contacted with B liquid and the amount of B liquid, promptly the equivalents of the alkali in the B liquid is preferably 2.6～3.5 amount with respect to the molal quantity (molal quantity of the equivalents/phosphorus atoms of alkali) of the phosphorus atoms in the A liquid, is preferably 2.8～3.2 amount especially.Equivalents through making the alkali in the B liquid is in the above-mentioned scope with respect to the molal quantity of the phosphorus atoms in the A liquid, and the ratio of components of the Li in the co-precipitation body, Fe and P is easily near 1: 1: 1.
In first operation, the contact temperature when A liquid is contacted with B liquid is 10～100 ℃, is preferably 30～100 ℃.Through A liquid is in the above-mentioned scope with the temperature that contacts of B liquid, the lithium composition in the reaction solution becomes and separates out easily.On the other hand, if A liquid is lower than above-mentioned scope, the trend that then exists the lithium composition in the solution to be difficult to separate out with the temperature that contacts of B liquid; In addition, if surpass above-mentioned scope, because solution boiling under the normal pressure, so cause liquid phase reactor to become difficult easily.
Wherein, the lithium source of in the modulation of A liquid and B liquid, using, divalent source of iron, source of phosphoric acid and alkali source can be aqueous, also can be anhydrides.In addition, from obtaining the viewpoint of the Phosphorus compound oxide carbon complex of highly purified lithium iron, the preferred few material of impurity content.
In first operation; PH is controlled at 5.5～9.5; And one side interpolation A liquid in water (C liquid), in C liquid add B liquid on one side, A liquid is contacted with B liquid react; Obtain containing the method (the following contact method A that also is recited as) of the co-precipitation body of lithium, iron and phosphorus, the pH control when A liquid contacts with B liquid easily and the viewpoint that increases of the yield of co-precipitation body preferred.Wherein, in the present invention, so-called " in C liquid, add A liquid on one side, in C liquid add on one side B liquid " refers to that to add the time of A liquid to C liquid overlapping wholly or in part with the time of adding B liquid to C liquid.And the composition adjustment of the Li from the co-precipitation body, Fe and P becomes and is easy to viewpoint, and is preferably overlapping fully with the time of adding B liquid to C liquid to the time of C liquid interpolation A liquid; Promptly; The interpolation of A liquid begins interpolation with B liquid and begins to be simultaneously, and the interpolation of A liquid finishes interpolation with B liquid and finish to be the while, but so long as do not damage the degree of effect of the present invention; Can be not exclusively overlapping, can in the process of adding A liquid, add B liquid at least.
The C liquid of contact method A is water, also can contain water-soluble reducing agents such as ascorbic acid, phenol, pyrogallol.
In contact method A, the amount of C liquid can be in reaction vessel C liquid by well-beaten amount.
In contact method A, the ratio of the addition of A liquid and the addition of B liquid, promptly the equivalents of the alkali in the B liquid is preferably 2.6～3.5 amount with respect to the molal quantity (molal quantity of the equivalents/phosphorus atoms of alkali) of the phosphorus atoms in the A liquid, is preferably 2.8～3.2 amount especially.Equivalents through making the alkali in the B liquid is in the above-mentioned scope with respect to the molal quantity of the phosphorus atoms in the A liquid, and the ratio of components of the Li in the co-precipitation body, Fe and P is easily near 1: 1: 1.
In contact method A, the temperature of the reaction solution (C liquid) when in reaction solution (C liquid), adding A liquid and B liquid is 10～100 ℃, is preferably 30～100 ℃.The temperature of the reaction solution (C liquid) when adding A liquid and B liquid through making is in the above-mentioned scope, and the lithium composition in the reaction solution becomes and separates out easily.On the other hand; If the temperature of the reaction solution (C liquid) when in reaction solution (C liquid), adding A liquid and B liquid is lower than above-mentioned scope; The trend that then exists the lithium composition in the reaction solution to be difficult to separate out; If surpass above-mentioned scope in addition, because solution boiling under the normal pressure, so cause liquid phase reactor to become difficult easily.
In contact method A; A liquid is to the adding method and the not special restriction of interpolation speed of reaction solution (C liquid); But near 1: 1: 1 and can access the viewpoint that batch differences is the material of stay in grade less, preferred stirring reaction solution (C liquid) on one side drips A liquid with certain speed on one side from the ratio of components of Li, Fe and P.And B liquid is preferably to the adding method and the interpolation speed of reaction solution (C liquid), Yi Bian use control such as pH control device rate of addition, makes the pH of reaction solution (C liquid) remain on the value of regulation, Yi Bian carry out the dropping of B liquid to reaction solution (C liquid).
In contact method A, after the interpolation of A liquid and B liquid finishes, can proceed still to keep the temperature of reaction solution (C liquid) to continue the slaking of stirring.Through carrying out this slaking, can reduce the unreacted elemental composition of reaction solution in mutually.The pH of the reaction solution when carrying out slaking (C liquid) is preferably 5.5～9.5, is preferably 5.5～8.5 especially.The pH of the reaction solution when carrying out slaking through making (C liquid) is in the above-mentioned scope, and the lithium composition of separating out is difficult to stripping again, and the ferrous components of separating out is difficult to oxidized.On the other hand, if the pH of the reaction solution (C liquid) when carrying out slaking is lower than above-mentioned scope, the lithium composition of then separating out stripping more easily, in addition, if surpass above-mentioned scope, the easy oxidation of the ferrous components of then separating out.Curing temperature when carrying out slaking is 10～100 ℃, is preferably 30～100 ℃.Through curing temperature is in the above-mentioned scope, obtain reducing the reaction solution effect of middle unreacted component mutually easily.On the other hand,, then there is the minimizing reaction solution trend of the effect reduction of middle unreacted component mutually if curing temperature is lower than above-mentioned scope, in addition, if surpass above-mentioned scope, then because solution seethes with excitement under the normal pressure, so cause liquid phase reactor to become difficult easily.
In contact method A, when C liquid adds A liquid with B liquid, can one side in reaction solution (C liquid) inertness gas such as nitrogen injection, Yi Bian carry out the interpolation of A liquid and B liquid.In addition, in contact method A, can make reducing agents such as ascorbic acid, phenol, pyrogallol be preferably ascorbic acid and in A liquid (solution that contains divalent iron ion and phosphate anion), coexist, carry out the interpolation of A liquid and B liquid.When adding A liquid and B liquid, in reaction solution (C liquid), inject inertness gas or make reducing agent, or, can prevent the oxidation of the Fe in the reaction solution (C liquid) by the two in C liquid (reaction solution) coexistence.Reducing agent is to the addition of A liquid, and the viewpoint from efficient is reacted well is preferably 0.1～2.0 quality % with respect to A liquid, is preferably 0.5～1.5 quality % especially.
In first operation, after the contacting of A liquid and B liquid finished, utilize usual method to carry out Separation of Solid and Liquid, reclaim the solids that obtains, wash as required, drying, obtain the co-precipitation body.Wherein, contain in use under the situation of material as alkali source of sodium or potassium, residual if alkali metal becomes impurity, then can't obtain LiFePO in the X-ray diffraction analysis
4The single-phase Phosphorus compound oxide carbon complex of lithium iron, so, preferably fully to wash, sodium in the co-precipitation body and potassium content are below the 0.5 quality %, are preferably below the 0.1 quality %.In addition, the baking temperature when carrying out co-precipitation body dry, good and divalent ferrous components is difficult to oxidized viewpoint from drying efficiency, is preferably 35～60 ℃.On the other hand, if the baking temperature of co-precipitation body is lower than 35 ℃, then drying is too time-consuming, and in addition, if surpass 60 ℃, then divalent iron is oxidized easily.
Second operation of the manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron of the present invention is to be blended in co-precipitation body and the conductive carbon material that obtains in first operation, the operation that obtains firing raw mix.
Conductive carbon material as second operation; For example; Can enumerate out native graphite or the such graphite of Delanium such as flaky graphite, flaky graphite and amorphous graphite; Carbon black classes such as carbon black, acetylene carbon black, Ketjen black, channel black, furnace black, dim, pyrolytic carbon black, carbon fiber etc.In addition, as the conductive carbon material of second operation, also can enumerate out through the organic carbon compound that carbon is separated out of firing in the 3rd operation.In addition, conductive carbon material can use a kind, also can be also with more than 2 kinds.Wherein, obtain the viewpoint of particulate matter from the industry easily, preferred carbon black, Ketjen black.
The average grain diameter of conductive carbon material is below the 1 μ m, is preferably below the 0.1 μ m, is preferably 0.01～0.1 μ m especially.In addition, when being fibrous, the average fiber of this conductive carbon material directly is below the 1 μ m, is preferably below the 0.1 μ m, is preferably 0.01～0.1um especially at conductive carbon material.Average grain diameter or average fiber through making conductive carbon material directly are in the above-mentioned scope, can make conductive carbon material high degree of dispersion in the particle of the Phosphorus composite oxides of lithium iron easily.Wherein, In the present invention; The average grain diameter of conductive carbon material or average fiber directly are average grain diameter or the average fiber footpaths of being obtained by scanning electron microscope photo (SEM), are the mean value in the fiber footpath of 20 particle grain size of from the scanning electron microscope photo, extracting out arbitrarily or fiber.
With fire before compare the trend that exists C atomic weight contained in the conductive carbon material to reduce slightly after firing.Therefore; In second operation; If conductive carbon material is 2～15 mass parts with respect to the use level of the co-precipitation body of 100 mass parts, be preferably 5～10 mass parts, then conductive carbon material is with respect to the use level of Phosphorus composite oxides 100 mass parts of the lithium iron in the Phosphorus compound oxide carbon complex of lithium iron; Being scaled the C atom becomes 1～12 mass parts easily, is preferably 3～8 mass parts.Through conductive carbon material is in the above-mentioned scope with respect to the use level of the co-precipitation body of 100 mass parts; When the Phosphorus compound oxide carbon complex of lithium iron is used as the positive active material of lithium secondary battery; Can give sufficient conductivity; So can reduce the internal resistance of lithium secondary battery, and the discharge capacity of unit mass or volume increases.On the other hand, if conductive carbon material is lower than above-mentioned scope with respect to the use level of the co-precipitation body of 100 mass parts, when then the Phosphorus compound oxide carbon complex of lithium iron being used as the positive active material of lithium secondary battery; Because can not fully give conductivity; So the internal resistance of lithium secondary battery raises easily, in addition; If surpass above-mentioned scope, then the discharge capacity of unit mass or volume reduces easily.
In second operation, preferably adopt dry type fully to mix, co-precipitation body and conductive carbon material are evenly mixed.In second operation; Be used for device that the co-precipitation body mixes with conductive carbon material etc.; As long as can access and fire raw mix uniformly; Not special restriction for example, can be enumerated out high speed puddle mixer (high speed mixer), high-speed mixer (supermixer), turbine ball mixer (タ one ボ ス Off
エア ミ キ サ one), devices such as Henschel mixer, nauta mixer and spiral ribbon agitator.Wherein, the even married operation of these co-precipitation bodies and conductive carbon material is not limited to illustrative mechanical device.
The 3rd operation is in the inertness atmosphere, to fire firing raw mix, obtaining the operation of the Phosphorus compound oxide carbon complex of lithium iron of in second operation, obtaining.
In the 3rd operation,, in inertness atmospheres such as nitrogen, argon, fire firing of raw mix in order to prevent the oxidation of Fe element.
In the 3rd operation, the firing temperature when firing firing raw mix is 500～800 ℃, is preferably 550～750 ℃.Through making the firing temperature of firing raw mix be in the above-mentioned scope LiFePO
4Crystallinity increase, so discharge capacity increase, and, be difficult to carry out particle diameter growth, so discharge capacity increases.On the other hand, be lower than above-mentioned scope, then LiFePO if fire the firing temperature of raw mix
4The low and discharge capacity of crystallinity reduce easily, in addition,, then exist and carry out the trend that particle diameter growth, discharge capacity reduce if surpass above-mentioned scope.In addition, the firing time of firing raw mix is more than 1 hour, is preferably 2～10 hours.In addition, in the 3rd operation, as required, can carry out firing more than 2 times, also can the material after once firing be pulverized, and then fire from making the uniform purpose of powder characteristics.
In the 3rd operation, fire the firing of raw mix after, suitably thing is fired in cooling, pulverizes as required or classification, obtains the Phosphorus compound oxide carbon complex of lithium iron.Wherein, in order to prevent the oxidation of Fe element, preferably in the inertness atmosphere, fire the cooling of thing.In addition, the pulverizing of carrying out as required of firing thing does, is that the situation of crisp block is inferior firing the Phosphorus compound oxide carbon complex of lithium iron that obtains, the pulverizing of suitably firing thing.
The LiFePO of the Phosphorus compound oxide carbon complex of lithium iron that carries out the manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron of the present invention and obtain
4Particle and fine conductive carbon material evenly disperse.And, carry out the manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron of the present invention and Phosphorus composite oxides of lithium iron in the Phosphorus compound oxide carbon complex of lithium iron that obtains, in X-ray diffraction analysis single-phase LiFePO
4And; The Phosphorus compound oxide carbon complex of lithium iron that carries out the manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron of the present invention and obtain is the homogeneous mixture of Phosphorus composite oxide particle of lithium iron and fine conductive carbon material; Utilize scanning electron microscope to observe (SEM); Can visually distinguish Phosphorus composite oxide particle of lithium iron and conductive carbon material; The average grain diameter of the Phosphorus composite oxide particle of being obtained by the SEM photo of lithium iron itself is 0.05～1 μ m, is preferably 0.1～0.5 μ m.Wherein, In the present invention; The average grain diameter of the Phosphorus composite oxides of lithium iron in the Phosphorus compound oxide carbon complex of lithium iron is average grain diameters of being obtained by scanning electron microscope photo (SEM), is the mean value of any 20 grain diameters extracting out from the scanning electron microscope photo.
And in the manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron of the present invention, the adjustment of the composition of the Phosphorus composite oxides of lithium iron in the Phosphorus compound oxide carbon complex of lithium iron easily.
The Phosphorus compound oxide carbon complex of lithium iron that carries out the manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron of the present invention and obtain, suitable to by positive pole, negative pole, spacer with contain the positive active material of the lithium secondary battery that the nonaqueous electrolyte of lithium salts constitutes.Wherein, Because the Phosphorus compound oxide carbon complex of lithium iron has moisture absorption; So in moisture is under the situation more than the 2000ppm, before the Phosphorus composite oxides of lithium iron are used as positive active material, preferably implement operations such as vacuumize; The moisture that makes the Phosphorus composite oxides of lithium iron is below the 2000ppm, to be preferably below the 1500ppm.
In addition; The Phosphorus composite oxides of lithium iron and known other lithium-transition metal composite oxide through the manufacturing approach that will carry out the Phosphorus compound oxide carbon complex of lithium iron of the present invention obtains are also used use, the fail safe that can further improve the lithium secondary battery that uses existing lithium-transition metal composite oxide.As the Phosphorus composite oxides of lithium iron that can obtain and the lithium transition-metal oxide of usefulness, can enumerate out the lithium-transition metal composite oxide shown in the formula (1) with the manufacturing approach of carrying out the Phosphorus compound oxide carbon complex of lithium iron of the present invention.
Li
aM
1-bA
bO
c (1)
(in the formula; M representes to be selected from the transition metal more than at least a kind among Co, the Ni; A representes to be selected from the metallic element more than at least a kind among Mg, Al, Mn, Ti, Zr, Fe, Cu, Zn, Sn, the In, and a representes that 0.9≤a≤1.1, b represent that 0≤b≤0.5, c represent 1.8≤c≤2.2.) example of the lithium-transition metal composite oxide kind shown in the above-mentioned general formula of illustration (1), can enumerate out LiCoO
2, LiNiO
2, LiNi
0.8Co
0.2O
2, LiNi
0.8Co
0.1Mn
0.1O
2, LiNi
0.4Co
0.3Mn
0.3O
2Deng.These lithium-transition metal composite oxides can be a kind, also can be more than 2 kinds.Not special restriction such as the rerum natura of the Phosphorus composite oxides of lithium iron that can obtain and the lithium-transition metal composite oxide of usefulness with the manufacturing approach of the Phosphorus compound oxide carbon complex of inventing of lithium iron; Average grain diameter is preferably 1～20 μ m; Be preferably 1～15 μ m especially, further be preferably 2～10 μ m; The BET specific area is preferably 0.1～2.0m
2/ g is preferably 0.2～1.5m especially
2/ g further is preferably 0.3～1.0m
2/ g.
The manufacturing approach that contains the co-precipitation body of lithium, iron and phosphorus of the present invention comprises pH is controlled at 5.5～9.5; And the solution (A liquid) that contains lithium ion, divalent iron ion and phosphate anion is contacted with containing aqueous slkali (B liquid), obtain containing the operation of the co-precipitation body of lithium, iron and phosphorus.
That is, the manufacturing approach of the co-precipitation body that contains lithium, iron and phosphorus of the present invention is identical with first operation of the manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron of the invention described above.And; The manufacturing approach that contains the co-precipitation body of lithium, iron and phosphorus of the present invention is controlled at 5.5～9.5 with pH, and makes the solution (A liquid) that contains lithium ion, divalent iron ion and phosphate anion and contain aqueous slkali (B liquid) and contact; React; Can easily contain the composition adjustment of Li, Fe and P in the co-precipitation body of lithium, iron and phosphorus, the ratio of components that can make Li, Fe and P is near 1: 1: 1, and can obtain the co-precipitation body with high yield.
Embodiment
Below, utilize embodiment that the present invention at length is described, but the present invention is not limited to these embodiment.
(embodiment 1)
(first operation)
< modulation of A liquid >
The 75 weight % phosphoric acid of dissolving 9.7g lithium sulfate in the 231ml pure water (0.075 mole, be scaled the Li atom be 0.15 mole), 39.7g ferrous sulfate 7 hydrates (0.15 mole, be scaled divalent Fe atom be 0.15 mole) and 19.6g (0.15 mole, be scaled the P atom be 0.15 mole) are modulated A1 liquid.
< modulation of B liquid >
Dissolving 19.1g lithium hydroxide 1 water salt (0.45 mole, 0.45 equivalent) in the 131ml pure water, modulation B1 liquid.
< A liquid contacts with B liquid >
In reaction vessel, add 250ml pure water (C liquid), be heated to 70 ℃.With the pH of reaction solution (C liquid) be controlled at 7, temperature is controlled at 70 ℃, stirring reaction solution is simultaneously with dripping all the A liquid and the B liquid of amount in 41 fens clockwise reaction vessels simultaneously.Then, adopt usual method to carry out Separation of Solid and Liquid, solids 50 ℃ of dryings 10 hours, is obtained the 28g sediment.
The sediment that obtains is carried out XRD determining and ICP mensuration, and the sediment that obtains is to contain ferrous phosphate 8 hydrates of lithium, iron and phosphorus and the co-precipitation body of lithium phosphate with 0.8: 1: 1 ratio of mol ratio.
(second operation)
Then, adopt dry type fully to mix co-precipitation body and the 0.8g carbon black (average grain diameter 0.05 μ m) that 10g obtains, thing is uniformly mixed.
(the 3rd operation)
Then, in nitrogen atmosphere, the homogeneous mixture that obtains was fired 5 hours with 600 ℃.Then, still in nitrogen atmosphere, cool off, obtain the Phosphorus compound oxide carbon complex of lithium iron.
(embodiment 2)
(first operation)
< modulation of A liquid >
With embodiment 1 same operation modulation A1 liquid.
< modulation of B liquid >
Dissolving 18.1g lithium hydroxide 1 water salt (0.45 mole, 0.45 equivalent) in the 131ml pure water, modulation B2 liquid.
< A liquid contacts with B liquid >
Use B2 liquid to replace B1 liquid, and with the pH of reaction solution be controlled at 5.5, temperature be controlled at 98 ℃ of replacements with the pH of reaction solution be controlled at 7, temperature is controlled at 70 ℃, in addition, operates equally with embodiment 1, obtains the 27g sediment.
The sediment that obtains is carried out XRD determining and ICP mensuration, and the sediment that obtains is to contain ferrous phosphate 8 hydrates of lithium, iron and phosphorus and the co-precipitation body of lithium phosphate with 0.9: 1: 1 ratio of mol ratio.
< second operation and the 3rd operation >
Operate equally with embodiment 1, obtain the Phosphorus compound oxide carbon complex of lithium iron.
(embodiment 3)
(first operation)
< modulation of A liquid >
With embodiment 1 same operation modulation A1 liquid.
< modulation of B liquid >
Dissolving 19.7g lithium hydroxide 1 water salt (0.47 mole, 0.47 equivalent) in the 136ml pure water, modulation B3 liquid.
< A liquid contacts with B liquid >
Use B3 liquid to replace B1 liquid, and with the pH of reaction solution be controlled at 8.5, temperature be controlled at 50 ℃ of replacements with the pH of reaction solution be controlled at 7, temperature is controlled at 70 ℃, in addition, operates equally with embodiment 1, obtains the 29g sediment.
The sediment that obtains is carried out XRD determining and ICP mensuration, and the sediment that obtains is to contain ferrous phosphate 8 hydrates of lithium, iron and phosphorus and the co-precipitation body of lithium phosphate with 1.1: 1: 1 ratio of mol ratio.
< second operation and the 3rd operation >
Operate equally with embodiment 1, obtain the Phosphorus compound oxide carbon complex of lithium iron.
(embodiment 4)
(first operation)
< modulation of A liquid >
The 75 weight % phosphoric acid of dissolving 9.7g lithium sulfate, 39.7g ferrous sulfate 7 hydrates and 19.6g add the L-ascorbic acid of 3g as reducing agent again in the 231ml pure water, modulation A2 liquid.
< modulation of B liquid >
With embodiment 1 same operation modulation B1 liquid.
< A liquid contacts with B liquid >
In reaction vessel, add 250ml pure water (C liquid), be heated to 70 ℃.With the pH of reaction solution (C liquid) be controlled at 7, temperature is controlled at 70 ℃, on one side in reaction system, be blown into nitrogen, stirring reaction solution on one side, and with dripping A liquid and the B liquid of all measuring in 41 fens clockwise reaction vessels simultaneously.Then, adopt usual method to carry out Separation of Solid and Liquid, solids 50 ℃ of dryings 10 hours, is obtained the 28g sediment.
The sediment that obtains is carried out XRD determining and ICP mensuration, and the sediment that obtains is to contain ferrous phosphate 8 hydrates of lithium, iron and phosphorus and the co-precipitation body of lithium phosphate with 0.9: 1: 1 ratio of mol ratio.
< second operation and the 3rd operation >
Operate equally with embodiment 1, obtain the Phosphorus compound oxide carbon complex of lithium iron.
(comparative example 1)
(first operation)
< modulation of the modulation of A liquid and B liquid >
With embodiment 1 same operation modulation A1 liquid and B1 liquid.
< A liquid contacts with B liquid >
In reaction vessel, add A1 liquid, stir, the B1 liquid of all measuring with dropping in 37 fens clockwise reaction vessels with certain speed simultaneously at 70 ℃.At this moment, the pH that drips the preceding A1 liquid of B1 liquid is 1, and the pH that drips the reaction solution after B1 liquid finishes is 7.After the B1 drop adds end, adopt usual method to carry out Separation of Solid and Liquid, solids 50 ℃ of dryings 10 hours, is obtained the 27g sediment.
The sediment that obtains being carried out ICP measure and XRD determining, is to contain ferrous phosphate 8 hydrates of lithium, iron and phosphorus and the co-precipitation body of lithium phosphate with 0.7: 1: 1 ratio of mol ratio.
< second operation and the 3rd operation >
Operate equally with embodiment 1, obtain the Phosphorus compound oxide carbon complex of lithium iron.
(comparative example 2)
(first operation)
< modulation of A liquid >
With embodiment 1 same operation modulation A1 liquid.
< modulation of B liquid >
Dissolving 16.9g lithium hydroxide 1 water salt (0.4 mole, 0.4 equivalent) in the 117ml pure water, modulation B4 liquid.
< A liquid contacts with B liquid >
Use B4 liquid to replace B1 liquid, and with the pH of reaction solution be controlled at 5, temperature be controlled at 98 ℃ of replacements with the pH of reaction solution be controlled at 7, temperature is controlled at 70 ℃, in addition, operates equally with embodiment 1, obtains the 24g sediment.
The sediment that obtains is carried out XRD determining and ICP mensuration, and the sediment that obtains is to contain ferrous phosphate 8 hydrates of lithium, iron and phosphorus and the co-precipitation body of lithium phosphate with 0.4: 1.1: 1 ratio of mol ratio.
< second operation and the 3rd operation >
Operate equally with embodiment 1, obtain the Phosphorus compound oxide carbon complex of lithium iron.
(comparative example 3)
(first operation)
< modulation of A liquid >
With embodiment 1 same operation modulation A1 liquid.
< modulation of B liquid >
Dissolving 30.6g lithium hydroxide 1 water salt (0.73 mole, 0.73 equivalent) in the 212ml pure water, modulation B5 liquid.
< A liquid contacts with B liquid >
Use B5 liquid to replace B1 liquid, and with the pH of reaction solution be controlled at 10, temperature be controlled at 70 ℃ of replacements with the pH of reaction solution be controlled at 7, temperature is controlled at 70 ℃, in addition, operates equally with embodiment 1, obtains the 33g sediment.
The sediment that obtains is carried out ICP measure, contain lithium, iron and phosphorus with 2.8: 1: 1 ratio of mol ratio.Only observe the peak of lithium phosphate from XRD determining.
< second operation and the 3rd operation >
Operate equally with embodiment 1, obtain the Phosphorus compound oxide carbon complex of lithium iron.
(comparative example 4)
(first operation)
< modulation of A liquid >
With embodiment 1 same operation modulation A1 liquid.
< modulation of B liquid >
The 25 quality % NaOH (0.41 mole, 0.41 equivalent) of dissolving 65.2g in the 37ml pure water, modulation B6 liquid.
< A liquid contacts with B liquid >
In reaction vessel, add A1 liquid, stir, the B6 liquid of all measuring with dropping in 27 fens clockwise reaction vessels with certain speed simultaneously at 70 ℃.At this moment, the pH that drips the preceding A1 liquid of B6 liquid is 1, and the pH that drips the reaction solution after B6 liquid finishes is 7.After the B6 drop adds end, adopt usual method to carry out Separation of Solid and Liquid, solids 50 ℃ of dryings 10 hours, is obtained the 25g sediment.
The sediment that obtains being carried out ICP measure and XRD determining, is to contain ferrous phosphate 8 hydrates of lithium, iron and phosphorus and the co-precipitation body of lithium phosphate with 0.4: 1.2: 1 ratio of mol ratio.
< second operation and the 3rd operation >
Operate equally with embodiment 1, obtain the Phosphorus compound oxide carbon complex of lithium iron.
[table 1]
1) yield in the table 1 is obtained with respect to the percentage of the co-precipitation physique amount of the calculating of the one-tenth component from A liquid with the actual sediment quality that obtains.
2) be changed to interpolation end back pH7 from adding preceding pH1.
< evaluation of physical property of the Phosphorus compound oxide carbon complex of lithium iron >
For the Phosphorus compound oxide carbon complex of lithium iron that in embodiment 1～3 and comparative example 1～4, obtains; Measure the average grain diameter of the Phosphorus composite oxides of lithium iron in the Phosphorus compound oxide carbon complex of lithium iron and the content of conductive carbon material; And, carry out X-ray diffraction analysis.The result that expression obtains in table 2.And, in Fig. 1 (embodiment 1) and Fig. 2 (comparative example 1), be illustrated in the X-ray diffractogram of the Phosphorus compound oxide carbon complex of lithium iron that obtains in embodiment 1 and the comparative example 1.Wherein, average grain diameter is to utilize the mean value of particle diameter of 20 Phosphorus composite oxides of lithium iron of any extraction in the Phosphorus compound oxide carbon complex of lithium iron of scanning electron microscope (SEM) itself.Conductive carbon material content is the C atom content.
[table 2]
| Average grain diameter (μ m) | C atom content (weight %) | The result of X-ray diffraction | |
| Embodiment 1 | ?0.20 | ?7.0 | LiFePO
4Single- |
| Embodiment | |||
| 2 | ?0.26 | ?7.0 | LiFePO 4Single-phase |
| Embodiment 3 | ?0.17 | ?7.5 | LiFePO 4Single-phase |
| Embodiment 4 | ?0.20 | ?7.1 | LiFePO 4Single-phase |
| Comparative example 1 | ?0.32 | ?6.3 | LiFePO 4、Fe 2P 2O 7 |
| Comparative example 2 | ?0.19 | ?7.8 | LiFePO 4、Fe 3(PO 4) 2 |
| Comparative example 3 | ?0.26 | ?7.3 | Li 3PO 4、Fe 3O 4 |
| Comparative example 4 | ?0.28 | ?6.2 | LiFePO 4、Fe 3(PO 4) 2、 Na 2Fe 3(PO 4) 3 |
< evaluation of battery performance >
<battery performance test >
(I) making of lithium secondary battery
Mix the embodiment 1～3 of manufacturing as stated and the Phosphorus compound oxide carbon complex 91 quality % of lithium iron, powdered graphite 6 quality % and the Kynoar 3 quality % of comparative example 1～4; As anodal agent; It is scattered in the N-N-methyl-2-2-pyrrolidone N-, modulates mixing cream.The mixing cream that coating obtains on aluminium foil carries out drying, punching press then, and punching on diameter 15mm disk obtains positive plate.
Use this positive plate, use each parts such as spacer, negative pole, positive pole, collector plate, installation accessory, outside terminal, electrolyte, make lithium secondary battery.Wherein, negative pole uses metallic lithium foil, and electrolyte uses and in 1: 1 mixing liquid of 1 liter of ethylene carbonate and methyl ethyl carbonate, is dissolved with 1 mole of LiPF
6Mixed liquor.
(II) performance evaluation of battery
In room temperature the lithium secondary battery of making is moved, measure discharge capacity.And, calculate with respect to LiFePO by following formula (2)
4The ratio of theoretical discharge capacity (170mAH/g).Its result of expression in table 3.
Ratio=[discharge capacity/LiFePO with respect to theoretical discharge capacity
4Theoretical discharge capacity (170mAH/g)] * 100 (2)
[table 3]
| Discharge capacity (mAH/g) | Ratio (%) with respect to theoretical discharge capacity | |
| Embodiment 1 | 163 | 96 |
| |
170 | 100 |
| Embodiment 3 | 149 | 88 |
| Embodiment 4 | 164 | 96 |
| Comparative example 1 | 122 | 72 |
| Comparative example 2 | 60 | 35 |
| Comparative example 3 | 11 | 6 |
| Comparative example 4 | 53 | 31 |
Claims (4)
1. the manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron is characterized in that, comprising:
First operation; PH is controlled at 5.5～9.5, and on one side in water C liquid, adds the solution A liquid that contains lithium ion, divalent iron ion and phosphate anion, in this C liquid add and contain aqueous slkali B liquid on one side; A liquid is contacted with B liquid, obtain containing the co-precipitation body of lithium, iron and phosphorus;
Second operation is mixed this co-precipitation body and conductive carbon material, obtains firing raw mix; With
The 3rd operation in the inertness atmosphere, is fired raw mix to this and is fired, and obtains the Phosphorus compound oxide carbon complex of lithium iron,
Wherein, the pH of said A liquid is below 2.5,
Contact temperature when said A liquid is contacted with said B liquid is 10～100 ℃.
2. the manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron as claimed in claim 1 is characterized in that, the contained alkali of said B liquid is lithium hydroxide.
3. according to claim 1 or claim 2 the manufacturing approach of the Phosphorus compound oxide carbon complex of lithium iron is characterized in that in said the 3rd operation, the said firing temperature of firing raw mix is 500～800 ℃.
4. manufacturing approach that contains the co-precipitation body of lithium, iron and phosphorus; It is characterized in that, comprise pH is controlled at 5.5～9.5, and in water C liquid, add the solution A liquid that contains lithium ion, divalent iron ion and phosphate anion on one side; In this C liquid, add on one side and contain aqueous slkali B liquid; A liquid is contacted with B liquid, obtain containing the operation of the co-precipitation body of lithium, iron and phosphorus
Wherein, the pH of said A liquid is below 2.5,
Contact temperature when said A liquid is contacted with said B liquid is 10～100 ℃.
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| JP2008183436A JP5323410B2 (en) | 2007-07-27 | 2008-07-15 | Method for producing lithium iron phosphorus-based composite oxide carbon composite and method for producing coprecipitate containing lithium, iron and phosphorus |
| JP2008-183436 | 2008-07-15 | ||
| JP2008183436 | 2008-07-15 |
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| JP5281765B2 (en) * | 2007-07-27 | 2013-09-04 | 日本化学工業株式会社 | Method for producing lithium iron phosphorus-based composite oxide carbon composite and method for producing coprecipitate containing lithium, iron and phosphorus |
| JP2010020987A (en) * | 2008-07-09 | 2010-01-28 | Sumitomo Chemical Co Ltd | Non-aqueous electrolyte secondary battery |
| CN102186769A (en) | 2008-10-22 | 2011-09-14 | 株式会社Lg化学 | Lithium iron phosphate having an olivine structure and analysis method thereof |
| WO2011043255A1 (en) * | 2009-10-06 | 2011-04-14 | 国立大学法人長岡技術科学大学 | Positive electrode material for lithium ion secondary battery, and process for production thereof |
| CN101777649A (en) * | 2010-03-15 | 2010-07-14 | 彩虹集团公司 | Preparation method of lithium iron phosphate of positive electrode material of lithium ion battery |
| JP5678685B2 (en) * | 2011-01-25 | 2015-03-04 | 住友金属鉱山株式会社 | Precursor of positive electrode active material for lithium secondary battery, method for producing the same, and method for producing positive electrode active material for lithium secondary battery |
| US8945498B2 (en) | 2011-03-18 | 2015-02-03 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing lithium-containing composite oxide |
| JP5709136B2 (en) * | 2011-09-05 | 2015-04-30 | 太平洋セメント株式会社 | Method for producing lithium iron phosphate and method for producing lithium iron phosphate-based positive electrode active material |
| CN103086343B (en) * | 2011-11-07 | 2015-03-25 | 湖北明申锂电科技有限公司 | Method for synthesizing lithium iron phosphate by liquid solid reduction |
| JP5776573B2 (en) * | 2012-02-06 | 2015-09-09 | 住友金属鉱山株式会社 | Positive electrode active material for lithium secondary battery and method for producing the same, precursor of the positive electrode active material and method for producing the same, and lithium secondary battery using the positive electrode active material |
| EP2698346A1 (en) * | 2012-08-14 | 2014-02-19 | Clariant International Ltd. | Mixed sulphate containing lithium-manganese-metal phosphate |
| JP6151386B2 (en) * | 2015-06-09 | 2017-06-21 | 太平洋セメント株式会社 | Manufacturing method of olivine type lithium phosphate positive electrode material |
| CN116057010A (en) * | 2020-09-04 | 2023-05-02 | 株式会社半导体能源研究所 | Method for producing positive electrode active material |
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| CN1514804A (en) * | 2001-04-10 | 2004-07-21 | �͵�-���ڱ�̫���ܺ������о������빫 | Binary, ternary and quaternary lithium phosphates, method for production thereof and use of the same |
| CN1837032A (en) * | 2005-10-14 | 2006-09-27 | 江苏大学 | Spherical porous high-density LiFePO4 powder and process for preparing same |
| CN1907844A (en) * | 2006-08-11 | 2007-02-07 | 广州市鹏辉电池有限公司 | High density ultrafine composite ferric lithium phosphate anode material and preparation method |
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| JP3890671B2 (en) * | 1997-04-22 | 2007-03-07 | 宇部興産株式会社 | Method for producing negative electrode material for non-aqueous electrolyte secondary battery, and negative electrode and battery using the same |
| JP4724912B2 (en) * | 2000-10-05 | 2011-07-13 | ソニー株式会社 | Method for producing positive electrode active material and method for producing non-aqueous electrolyte secondary battery |
| JP4475882B2 (en) * | 2003-03-31 | 2010-06-09 | 国立大学法人九州大学 | Method for producing positive electrode material for secondary battery, and secondary battery |
| DE102005012640B4 (en) * | 2005-03-18 | 2015-02-05 | Süd-Chemie Ip Gmbh & Co. Kg | Circular process for the wet-chemical production of lithium metal phosphates |
| BRPI0612557A2 (en) * | 2005-06-29 | 2012-02-28 | Umicore Nv | process for preparing crystalline lifepo4 powder, carbon-free, crystalline lifepo4 powder, use of it, and, electrode mixture for lithium secondary batteries with non-aqueous liquid electrolyte |
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| CN1514804A (en) * | 2001-04-10 | 2004-07-21 | �͵�-���ڱ�̫���ܺ������о������빫 | Binary, ternary and quaternary lithium phosphates, method for production thereof and use of the same |
| CN1837032A (en) * | 2005-10-14 | 2006-09-27 | 江苏大学 | Spherical porous high-density LiFePO4 powder and process for preparing same |
| CN1907844A (en) * | 2006-08-11 | 2007-02-07 | 广州市鹏辉电池有限公司 | High density ultrafine composite ferric lithium phosphate anode material and preparation method |
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