CN1299979C - Ferrous phosphate hydrated salt crystal, producing method thereof and method for producing Li-Fe-P composite oxides - Google Patents

Ferrous phosphate hydrated salt crystal, producing method thereof and method for producing Li-Fe-P composite oxides Download PDF

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CN1299979C
CN1299979C CNB031020941A CN03102094A CN1299979C CN 1299979 C CN1299979 C CN 1299979C CN B031020941 A CNB031020941 A CN B031020941A CN 03102094 A CN03102094 A CN 03102094A CN 1299979 C CN1299979 C CN 1299979C
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composite oxides
phosphorus series
series composite
iron phosphorus
manufacture method
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CN1435372A (en
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木下真之
仲冈泰裕
山崎信幸
根岸克幸
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Nippon Chemical Industrial Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The purpose of the invention is to prepare a fine ferrous phosphate hydrate crystal excellent in processability and suitable as a raw material for producing a functional inorganic material, particularly that for LiFePO<SB>4</SB>or LiFeMePO<SB>4</SB>(Me is at least one metal element selected from Mn, Co, Ni and Al) to be used for the positive material of a lithium secondary battery, and to provide a method for industrially advantageously producing the above crystal in a high yield and a production method for a lithium/iron/phosphorus-based complex oxide using the crystal. The ferrous phosphate hydrate crystal is represented by the formula: Fe<SB>3</SB>(PO<SB>4</SB>)<SB>2</SB>/8H<SB>2</SB>O and has an average particle size of 5 [mu]m or less. It is preferable that the crystal has a half value width of a diffraction peak in a lattice place (020 plane) obtained by an X-ray diffraction analysis of >=0.20[deg.].

Description

The manufacture method of ferrous phosphate hydrated salt crystal, its manufacture method and ithium iron phosphorus series composite oxides
Technical field
The present invention relates to as the purposes of the manufacturing raw material of functional inorganic material, the LiFePO that particularly uses as the positive active material of lithium battery 4Or LiFeMePO 4The manufacture method of ferrous phosphate hydrated salt crystal, its manufacture method and ithium iron phosphorus series composite oxides that the manufacturing raw material of (Me represents to be selected from least a among Mn, Co, Ni, the Al or more than one metallic element) is useful.
Background technology
In recent years, in household electrical appliances, along with portabilityization, wireless penetration progress by leaps and bounds, as the power supply of the miniature electric machine of laptop personal computer, portable phone, pick up camera etc., lithium-ions battery is just in practicability.About this lithium-ions battery, is useful report [" マ テ リ ア Le リ サ-チ Block レ テ イ Application " vol15 from proposition cobalts such as water island in 1980 acid lithium as the positive active material of lithium-ions battery, p783-789 (1980)] since, relate to the research and development of cobalt acid lithium actively, up to the present proposing many reports.
But Co is ubiquity not on earth, is scarce resource, and therefore the new positive active material of cobalt acid lithium is instead carrying out for example LiNiO 2, LiMn 2O 4, LiFeO 2, LiFePO 4Deng exploitation.
Wherein, LiFePO 4Have volume density and arrive 3.6g/cm greatly 3, the noble potential, the theoretical capacity that produce 3.4V also arrive the such feature of 170mAh/g greatly.And, except Fe is aboundresources and cheapness, with regard to LiFePO 4, state in the early stage, per 1 Fe atom contains 1 Li that can electrochemically break away from, and therefore instead the expectation of the positive active material of the new lithium battery of cobalt acid lithium is very big.
Propose with LiFePO 4The LiFePO that perhaps replaces the part of its Fe with other metal 4Lithium battery (for example, with reference to patent documentation 1～6) as positive active material.
As general LiFePO 4Manufacture method, for example propose, use the ferrous phosphate salt hydrate, according to following reaction formula (1)
[Chemical formula 1]
Reaction formula (1)
The method of making is used ironic oxalate, according to following reaction formula (2)
[Chemical formula 2]
Reaction formula (2)
The method of making is perhaps used ironic acetate, according to following reaction formula (3)
[chemical formula 3]
Reaction formula (3)
The method of making etc.
Wherein, use the method for ferrous phosphate salt hydrate, by product only is a water, therefore industrial be particularly advantageous.
This ferrous phosphate salt hydrate is to add (with reference to the non-patent literature 1) that ammonium hydrogen phosphate or sodium hydrogen phosphate are made in containing the aqueous solution of ferrous ion.
But, the ferrous phosphate salt hydrate that obtains in this way, median size is 7 μ m～tens of μ m, and its particulate crystallization is flourishing and stone.
Therefore, the shortcoming that existence reactivity difference and be difficult to pulverize etc. is processed.Its result is difficult to expand that positive active material as lithium battery uses with LiFePO 4The purposes of manufacturing raw material for the functional inorganic material of representative.
[patent documentation 1]
Te Kaiping 9-134724 communique
[patent documentation 2]
Te Kaiping 9-134725 communique
[patent documentation 3]
Te Kaiping 11-261394 communique
[patent documentation 4]
The spy opens the 2001-110414 communique
[patent documentation 5]
The spy opens the 2001-250555 communique
[patent documentation 6]
The spy opens the 2000-294238 communique
[non-patent literature 1]
" chemical voluminous dictionary 9 ", altogether uprightly publish, 1993, p.809～810, with reference to the tertiary iron phosphate hurdle.
Summary of the invention
The object of the present invention is to provide a kind of purposes of the manufacturing raw material of functional inorganic material, special LiFePO that uses with the positive active material of lithium battery of being suitable for 4And LiFeMePO 4The manufacturing raw material of (in the formula, Me represents to be selected from least a among Mn, Co, Ni and the Al or more than one metallic element) fine and ferrous phosphate hydrated salt crystal that processibility is good, the manufacture method of making the industrial advantageous method of this ferrous phosphate hydrated salt crystal and using the ithium iron phosphorus series composite oxides of this ferrous phosphate salt hydrate with high yield.
The inventor is in such practical situation, through research in depth repeatedly, found that, the ferrous phosphate hydrated salt crystal that adds alkali to react in the aqueous solution that contains divalent iron salt and phosphoric acid and obtain is the fine-grain with specified particle diameter, become the processibility that troubles prior art and reactive aspect all good crystal.
That is, the 1st invention of the present invention provides a kind of ferrous phosphate hydrated salt crystal, with general formula Fe 3(PO 4) 28H 2O represents, it is characterized in that: median size is below the 5 μ m.
Such ferrous phosphate hydrated salt crystal, the half breadth of the diffraction peak of the lattice plane of obtaining from X-ray diffraction analysis (020 face) is preferably more than 0.20 °, and is preferably especially below the 1 weight % as the content of the Na of impurity.
In addition, the 2nd invention of the present invention provides a kind of manufacture method of ferrous phosphate hydrated salt crystal, it is characterized in that: add alkali and react in the aqueous solution that contains divalent iron salt and phosphoric acid.
In addition, above-mentioned divalent iron salt is preferably ferrous sulfate heptahydrate (FeSO 47H 2O).
In addition, the 3rd invention of the present invention provides a kind of manufacture method of ithium iron phosphorus series composite oxides, it is characterized in that: with ferrous phosphate hydrated salt crystal, Trilithium phosphate and the conductive carbon material of (A) above-mentioned the 1st invention or (B) above-mentioned the 1st invention ferrous phosphate hydrated salt crystal, Trilithium phosphate, contain at least a of the metallic element that is selected among Mn, Co, Ni and the Al or more than one metallic compound and conductive carbon material and mix, fire.
The manufacture method of such ithium iron phosphorus series composite oxides, preferably include: with the ferrous phosphate hydrated salt crystal of (A) above-mentioned the 1st invention, Trilithium phosphate and conductive carbon material or (B) above-mentioned the 1st the invention the ferrous phosphate hydrated salt crystal, Trilithium phosphate, contain and be selected from Mn, Co, metallic element among Ni and the Al at least a or more than one metallic compound and conductive carbon material blended first operation, then, thereby resulting mixture is carried out second operation that pulverization process obtains reacting elementary thing with drying process, then, thus fire this and react the 3rd operation that elementary thing obtains the ithium iron phosphorus series composite oxides.
In addition, the operation that the elementary thing of resulting reaction is carried out extrusion forming preferably is set after above-mentioned second operation.
In addition, the median size of the preferred ithium iron phosphorus series composite oxides that generate is below the 0.5 μ m.
Description of drawings
Fig. 1 is the X-ray diffractogram of the ferrous phosphate hydrated salt crystal that obtained by embodiment 1.
Fig. 2 is the X-ray diffractogram of the ferrous phosphate hydrated salt crystal that obtained by comparative example 1.
Fig. 3 is the X-ray diffractogram of the ithium iron phosphorus series composite oxides that obtained by embodiment 4.
Embodiment
Below, explain the present invention.
Ferrous phosphate hydrated salt crystal of the present invention is with general formula Fe 3(PO 4) 28H 2Phosphoric acid that O represents industry iron hydrated salt crystal is characterized in that, the median size of being obtained by laser diffractometry is below the 5 μ m, be preferably 1～5 μ m.
In addition, ferrous phosphate hydrated salt crystal of the present invention is except that above-mentioned particle property, when using CuK α line as radioactive source this crystal to be carried out X-ray diffraction analysis, the half breadth of diffraction peak (020 face) is more than 0.20 ° near 2 θ=13.1, is preferably 0.2～0.4 °.Ferrous phosphate hydrated salt crystal of the present invention, because the half breadth of lattice plane (020 face) has characteristic such more than 0.20 °, therefore compare with existing ferrous phosphate hydrated salt crystal, crystallinity is low, be the softish crystallization, and the miniaturization that utilize to pulverize produces or also become good with other the reactivity of compound.
In addition, ferrous phosphate hydrated salt crystal of the present invention is at the LiFePO as the positive active material of lithium battery 4Or LiFeMePO 4When the manufacturing raw material of (Me represents to be selected from least a among Mn, Co, Ni and the Al or more than one metallic element) uses, as impurity, Na content is few more good more, but in the manufacture method of as described later ferrous phosphate hydrated salt crystal, as alkali source, under the situation of the compound that contains the Na composition that uses sodium hydroxide etc., for example this ferrous phosphate hydrated salt crystal and Trilithium phosphate are fired and made LiFePO 4The time, this Na forms sodium phosphate, and becomes the reason that battery performance is reduced, and therefore ferrous phosphate hydrated salt crystal of the present invention is below the 1 weight % as the Na content of this impurity, is preferably below the 0.8 weight %.
And then, ferrous phosphate hydrated salt crystal of the present invention except above-mentioned Na content, is below the 1 weight % if be selected from the total amount of the metal content among Ti, Mn, Zn, Cr, Ni, Cu, the Co, be preferably below the 0.8 weight %, and K, Ca, Mg, Al, Si, SO 4, Cl, NO 3Content Deng impurity is below the 1 weight %, is preferably below the 0.8 weight %, just can be suitable as the manufacturing raw material that requires highly purified functional inorganic material especially and use, and be gratifying especially therefore.
Below, the manufacture method of ferrous phosphate hydrated salt crystal of the present invention is described.
The manufacture method of ferrous phosphate hydrated salt crystal of the present invention is characterized in that, in the aqueous solution that contains divalent iron salt and phosphoric acid, adds alkali and reacts.
As the divalent iron salt that can use, for example can enumerate ferrous sulfate, iron protochloride, ironic acetate, ironic oxalate etc., these molysite can use a kind of or more than two kinds, in addition, these molysite can be hydrates, also can be anhydrides.Wherein, ferrous sulfate heptahydrate (FeSO 47H 2O) industrial can obtaining easily, and be cheap, be particularly preferred therefore.
As the phosphoric acid that can use, if industrial obtaining just has no particular limits.
Alkali as using has no particular limits, and for example can enumerate ammonia, ammoniacal liquor, caustic soda, Ke Xingjia, NaHCO 3, Na 2CO 3, K 2CO 3, KHCO 3, Ca (OH) 2, mineral alkali such as LiOH, perhaps organic bases such as thanomin etc., these alkali can use a kind of or more than two kinds.Wherein, sodium hydroxide obtains easily industrial, and is cheap, is particularly preferred therefore.
As concrete operation, at first, the aqueous solution of modulation dissolving divalent iron salt and phosphoric acid, making by phosphoric acid becomes 0.60～0.75 to the mol ratio of the iron atom in the divalent iron salt, is preferably 0.65～0.70.The concentration of aqueous solution of this moment if can dissolve divalent iron salt and concentration of phosphoric acid, just has no particular limits, but is more than the 0.1mol/L as divalent iron salt usually, is preferably 0.5～1.0mol/L.
Then, in this aqueous solution, add alkali, the ferrous phosphate hydrated salt crystal is separated out.The evolution reaction of ferrous phosphate hydrated salt crystal, the acceleration owing to the interpolation of this alkali.The addition of alkali by the mol ratio to divalent iron salt, is 1.8～2.0, is preferably 1.95～2.0.
The interpolation temperature of this alkali has no particular limits, and is generally 5～80 ℃, is preferably 15～35 ℃, and in addition, the speed of dripping of this alkali etc. also has no particular limits, but in order to obtain stable quality, preferably imports at leisure in the reaction system with certain speed of dripping.
After reaction finishes, utilize ordinary method to carry out solid-liquid separation, reclaim precipitate, clean, drying, as required, pulverize, classification, become goods.At resulting ferrous phosphate hydrated salt crystal (Fe 3(PO 4) 28H 2O) be under the situation such as fragile bonded bulk, the suitable pulverizing of carrying out as required again, but the crystal grain of ferrous phosphate hydrated salt crystal self is to have above-mentioned specific median size.That is, the median size that resulting ferrous phosphate hydrated salt crystal is obtained by laser diffractometry is below the 5 μ m, is preferably 1～5 μ m.
Moreover, just clean, preferably the clean fully Na content to the ferrous phosphate hydrated salt crystal of separating out of water is below the 1 weight %, is preferably below the 0.8 weight %.
In addition, just dry, drying needs the time less than 35 ℃ the time, if surpass 50 ℃, just causes the disengaging of ferrous oxidation or crystal water, therefore at 35～50 ℃, preferably carries out drying at 40～50 ℃.
The ferrous phosphate hydrated salt crystal that obtains like this, the median size of being obtained by laser diffractometry is below the 5 μ m, be preferably 1～5 μ m, and as best physicals, the half breadth of the diffraction peak of the lattice plane of being obtained by X-ray diffraction analysis (020 face) is more than 0.20 °, is preferably 0.20～0.40 °.And except above-mentioned physicals, Na content as impurity is below the 1 weight %, be preferably below the 0.8 weight %, and more preferably count below the 1 weight % by total amount as the metal content that is selected among Ti, Mn, Zn, Cr, Ni, Cu, the Co of impurity, be preferably below the 0.8 weight % K, Ca, Mg, Al, Si, SO 4, Cl, NO 3Content Deng impurity is below the 1 weight %, is preferably below the 0.8 weight %.
According to the manufacture method of ferrous phosphate hydrated salt crystal of the present invention because with Fe 3(PO 4) 28H 2The ratio that the composition of O is identical adds alkali in advance in the reaction system of iron and phosphorus coexistence, so when pH rises, cause the decomposition of phosphoric acid equably, react with the iron ion that coexists with the regulation ratio on every side, generates Fe equably 3(PO 4) 28H 2Therefore O becomes the situation that is difficult to cause grain growth, therefore thinks resulting crystallization, and particle diameter is little, and is reactive good.
Ferrous phosphate hydrated salt crystal of the present invention, particle diameter is little and reactive good, therefore can be suitable as the manufacturing raw material, special in LiFePO used in the positive active material of lithium battery of functional inorganic material 4Or LiFeMePO 4The manufacturing raw material of (Me represents to be selected from least a among Mn, Co, Ni and the Al or more than one metallic element) uses.
Below, the manufacture method of ithium iron phosphorus series composite oxides of the present invention is described.
The manufacture method of ithium iron phosphorus series composite oxides of the present invention, it is characterized in that, above-mentioned ferrous phosphate hydrated salt crystal, Trilithium phosphate and the mixing of conductive carbon material are fired (below, be called " manufacture method of A ") or with above-mentioned ferrous phosphate hydrated salt crystal, Trilithium phosphate, contain at least a of the metallic element that is selected among Mn, Co, Ni and the Al or more than one metallic compound and conductive carbon material and mix and fire (below, be called " manufacture method of B ").
In the manufacture method of the ithium iron phosphorus series composite oxides of above-mentioned A of the present invention and B, particularly including the ferrous phosphate hydrated salt crystal that (A) is above-mentioned, Trilithium phosphate and conductive carbon material or (B) above-mentioned ferrous phosphate hydrated salt crystal, Trilithium phosphate, contain and be selected from Mn, Co, metallic element among Ni and the Al at least a or more than one metallic compound and conductive carbon material blended first operation, then, thereby the mixture that obtains is carried out second operation that pulverization process obtains reacting elementary thing, then, thereby fire this and react the 3rd operation that elementary thing obtains the ithium iron phosphorus series composite oxides, especially under will the situation of resulting like this ithium iron phosphorus series composite oxides as the positive active material use of lithium battery, discharge capacity is improved, and is gratifying especially therefore.
According to the manufacture method of above-mentioned A, can access the LiFePO that coats the positive active material that is suitable as lithium battery with the conductive carbon material 4The ithium iron phosphorus series composite oxides of particle surface, in addition,, can access with the conductive carbon material and coat LiFeMePO according to the manufacture method of above-mentioned B 4The ithium iron phosphorus series composite oxides of the particle surface of (Me represents to be selected from least a among Mn, Co, Ni, the Al or more than one metallic element).
In above-mentioned first operation, the Trilithium phosphate (Li that can in the manufacture method of above-mentioned A and B, use 3PO 4), if industrial can access just has no particular limits, but,, be preferably below the 5 μ m if the median size of being obtained by laser diffractometry is below the 10 μ m, mixing will be carried out fully, and reactivity becomes well, is gratifying especially therefore.
As the conductive carbon material that can in the manufacture method of above-mentioned A and B, use, for example can enumerate graphite such as natural graphites such as flaky graphite, flaky graphite and amorphous graphite and electrographite, carbon black classes such as carbon black, acetylene black, high conductivity carbon black (ケ Star チ エ Application Block ラ Star Network), channel black, furnace black, dim, thermal black, carbon fibers etc., these conductive carbon materials can be with a kind of or use more than two kinds.Wherein, because the high conductivity carbon black is a particulate, obtain easily industrial, so be particularly preferred.
These conductive carbon materials if the median size of being obtained by electron micrograph is below the 1 μ m, are preferably below the 0.1 μ m, are preferably 0.01～0.1 μ m especially, just can be with high dispersion state attached to LiFePO 4Perhaps LiFeMePO 4The particle surface of (Me represents to be selected from least a among Mn, Co, Ni and the Al or more than one metallic element) is gratifying therefore.
As containing at least a of the metallic element from Mn, Co, Ni and the Al that can the manufacture method of above-mentioned B, use, selected or more than one metallic compound, can enumerate the oxide compound that contains these metallic elements, oxyhydroxide, nitrate, acetate, carbonate, phosphoric acid salt, organic acid salt etc., physicals as these metallic compounds, if the median size of being obtained by laser diffractometry is below the 10 μ m, be preferably below the 5 μ m, mixing will be carried out fully, and reactivity becomes well, is gratifying especially therefore.
Moreover, in the manufacture method of ithium iron phosphorus series composite oxides of the present invention, the ferrous phosphate hydrated salt crystal (Fe of above-mentioned raw materials 3(PO 4) 28H 2O), Trilithium phosphate, conductive carbon material and metallic compound, use highly purified above-mentioned substance, when the positive active material as lithium battery uses, be gratifying especially.
The operation of first operation is at first with (A) ferrous phosphate hydrated salt crystal (Fe 3(PO 4) 28H 2O), Trilithium phosphate (Li 3PO 4) and conductive carbon material or (B) ferrous phosphate hydrated salt crystal (Fe 3(PO 4) 28H 2O), Trilithium phosphate (Li 3PO 4), the metallic element that is selected among Mn, Co, Ni and the Al of conductive carbon material and containing at least a or more than one metallic compound measure in accordance with regulations and mix.
In the manufacture method of above-mentioned A, the proportioning of ferrous phosphate hydrated salt crystal and Trilithium phosphate, if count 0.9～1.1, be preferably 1.00～1.05, then obtaining LiFePO by the mol ratio (Li/Fe) of Fe atom in the ferrous phosphate hydrated salt crystal and the Li atom in the Trilithium phosphate 4Single-phase this aspect on be suitable, if this mol ratio less than 0.9 or surpass 1.1, with regard to the remained unreacted raw material, is inappropriate therefore.
In addition, in the manufacture method of above-mentioned B, the proportioning of the metallic element that ferrous phosphate hydrated salt crystal, Trilithium phosphate and containing is selected among Mn, Co, Ni and the Al at least a or more than one metallic compound, as the Fe atom in the ferrous phosphate hydrated salt crystal, Li atom in the Trilithium phosphate and the mol ratio of the atoms metal (Me) in the metallic compound, by Li/ (Fe+Me), if 0.9～1.1, be preferably 1.00～1.05, then obtaining LiFeMePO 4Single-phase this aspect on be specially suitable.
In addition, the conductive carbon material, with fire before compare, there is the tendency of some minimizings in the amount of the C atom that contains in firing back conductive carbon material, so use level of conductive carbon material, the total amount of relative ferrous phosphate hydrated salt crystal and Trilithium phosphate or ferrous phosphate hydrated salt crystal, Trilithium phosphate and metallic compound is if 0.08～15.5 weight % is preferably 3.8～9.5 weight %, then the covering amount of conductive carbon material is pressed with respect to LiFePO 4Perhaps LiFeMePO 4The C atom content of (Me represents to be selected from least a among Mn, Co, Ni and the Al or more than one metallic element) is 0.1～20 weight %, is preferably 5～12 weight %.In the use level of this conductive carbon material during less than 0.08 weight %, owing to can not give sufficient electroconductibility to the ithium iron phosphorus series composite oxides, so in the lithium battery of ithium iron phosphorus series composite oxides that obtains as positive active material, internal resistance rises, on the other hand, if surpass 15.5 weight %, the discharge capacity of every weight or volume reduces on the contrary, is worthless therefore.
Moreover, in first operation, when implementing second operation described later, preferably use mixing machine etc. to mix fully, so that each raw material mixes in advance equably with drying process.
In the manufacture method of above-mentioned A and B, thus second operation be reactive better in order to make, use pulverizer the mixture of these raw materials to be mixed fully and pulverization process obtains reacting the operation of elementary thing with drying process.
At this, the elementary thing of so-called above-mentioned reaction is in order to make (A) ferrous phosphate hydrated salt crystal (Fe 3(PO 4) 28H 2O), Trilithium phosphate (Li 3PO 4) and conductive carbon material or (B) ferrous phosphate hydrated salt crystal (Fe 3(PO 4) 28H 2O), Trilithium phosphate (Li 3PO 4), reactive good before the mixture of the metallic element that is selected among Mn, Co, Ni and the Al of conductive carbon material and containing at least a or more than one metallic compound the firing afterwards, in with each raw material high dispersive, the particle distance of each stock yard is positioned as close to, thereby improves the elementary thing of reaction of the contact area of each raw material.
In the present invention, if that the specific volume of the mixture after this pulverizing is 1.5ml/g is following, be preferably 1.0～1.4ml/g, then can be under 500～700 ℃ cryogenic firing temperature because of sintering does not cause grain growth, in X-ray diffraction analysis, owing to obtain at LiFePO yet 4Or LiFeMePO 4The monophasic particle surface of (Me represents to be selected from least a among Mn, Co, Ni and the Al or more than one metallic element) is the ithium iron phosphorus series composite oxides of coating conducting carbonaceous material equably, thus preferably with the mixture of the specific volume of this scope as the elementary thing of reaction.
Moreover the so-called specific volume among the present invention is based on the apparent density put down in writing among the JIS-K-5101 or the method for apparent specific volume, use the vibro-compaction method 10g sample of in the graduated cylinder of 50ml, packing into, jolt ramming 500 times and after leaving standstill, read volume, the specific volume of obtaining according to following formula.
[mathematical expression 1]
Specific volume (ml/g)=V/F
(in the formula, F represents the interior sample mass of handling (g) of receiver, and V represents the sample volume (ml) after the jolt ramming.)
In the manufacture method of ithium iron phosphorus series composite oxides of the present invention, the elementary thing of above-mentioned reaction, except specific volume is this scope, if the ferrous phosphate hydrated salt crystal of contained raw material is to be close to amorphous state in the elementary thing of this reaction, even be that purpose is when 500～700 ℃ low temperature is fired then to suppress growing up of particle diameter, reaction is also fully carried out, and obtains LiFePO 4Perhaps LiFeMePO 4Therefore (Me represents to be selected from least a among Mn, Co, Ni and the Al or more than one metallic element) single-phase be particularly preferred.
As the pulverizer that can use, be preferably pulverizer with strong shearing force, as pulverizer, preferably use rotary mill, vibrating mill, planet mill, vehicle agitator mill etc. with so strong shearing force.This pulverizer is to put into ball, bead etc. to pulverize vehicle, the pulverizer that the shearing friction effect of the thing that mainly utilizes the medium is pulverized in container.As such device, can use commercially available device.
Pulverizing vectorial particle diameter if 1～25mm just can pulverize fully, is desirable therefore.Pulverize vectorial material for this, ceramic beads such as zirconium white, aluminum oxide because hardness height, abrasion resistance are strong and can prevent metallic pollution to material, are particularly preferred therefore.
In addition, with regard to above-mentioned pulverizing vehicle, to pulverize vehicle in order in container, storing, and to manage shearing force and frictional force aptly by the circulating medium deposits yields with spatial volume 50～90%, the preferred operating condition of suitably adjusting pulverizer carries out pulverization process.
In addition, in the manufacture method of ithium iron phosphorus series composite oxides of the present invention, if as required, except that above-mentioned pulverization process, this is reacted elementary thing carry out the extrusion forming processing, and improve the contact area of each raw material, discharge capacity and cycle characteristics are improved more.Forming pressure, has no particular limits with Intake Quantity and different with press, but 5～200MPa normally.Use if press-forming machine can be suitable for hand press, Ingot pressing machine, briquetting press, roller molding machine etc., just have no particular limits.
Then, in the 3rd operation, the elementary thing of the reaction that obtains in second operation is fired.
Firing temperature is 500～700 ℃, is preferably 550～650 ℃.In the present invention so that this firing temperature in this scope and the ithium iron phosphorus series composite oxides that obtain as the lithium battery of positive active material, can improve discharge capacity and charging cycle characteristic.At firing temperature during less than 500 ℃, because reaction is carried out insufficiently, thereby the remained unreacted raw material, on the other hand,, carry out sintering as mentioned above like that if surpass 700 ℃, can cause grain growth, thereby be worthless.
Firing time is 2～20 hours, is preferably 5～10 hours.
Can be in inert gas atmospheres such as nitrogen, argon gas or reducing atmospheres such as hydrogen, carbon monoxide in any kind of atmosphere in fire, have no particular limits, but aspect the security when operation, preferably in inert gas atmospheres such as argon gas, carry out.In addition, as required, these are fired also and can carry out several times.
After firing, suitably cool off, as required, pulverize or classification, obtain coating LiFePO equably with the conductive carbon material 4Perhaps LiFeMePO 4The ithium iron phosphorus series composite oxides of the particle surface of (Me represents to be selected from least a among Mn, Co, Ni and the Al or more than one metallic element).In order to prevent the oxidation of Fe and Me element, preferably reducing atmospheres such as inert gas atmosphere such as formation argon gas or hydrogen, carbon monoxide cool off in reaction system.In addition, the ithium iron phosphorus series composite oxides that obtain firing are suitable the execution as required and pulverizing of carrying out under the situation such as fragile bonded bulk, but according to the manufacture method of the preferred implementation of ithium iron phosphorus series composite oxides of the present invention, the particle of ithium iron phosphorus series composite oxides self is to have following specific median size, the particle of BET specific surface area.That is, resulting ithium iron phosphorus series composite oxides, the median size of being obtained by electron scanning micrograph (SEM) is below the 0.5 μ m, is preferably 0.05～0.5 μ m, the BET specific surface area is 10～100m 2/ g is preferably 30～70m 2/ g.
The ithium iron phosphorus series composite oxides of the present invention that obtain like this can be suitable as by positive pole, negative pole, barrier film and the positive active material that contains the lithium battery that the nonaqueous electrolyte of lithium salts constitutes uses.
Under with the situation of these ithium iron phosphorus series composite oxides as positive active material, its form can be that median size is that the median size that the following primary particle set of the above 0.5 μ m of 0.05 μ m forms is the above primary particle aggregate to 75 μ m of 1 μ m.And, in an above-mentioned aggregate, more than 70% of full volumetric, the particle diameter that is preferably an aggregate more than 80% are preferably below the above 20 μ m of 1 μ m, in addition, these ithium iron phosphorus series composite oxides, if in atmosphere, pulverize etc., in resulting ithium iron phosphorus series composite oxides, owing to contain the above moisture of 3000ppm, therefore before using, to implement operations such as vacuum-drying as positive active material, make the moisture content of these ithium iron phosphorus series composite oxides reach 2000ppm following, be preferably below the 1500ppm and re-use.
In addition, by ithium iron phosphorus series composite oxides and known other lithium-cobalt system composite oxides, lithium-nickel-based compound oxide or lithium manganese system complex oxide and the usefulness that obtains with manufacture method of the present invention, can further improve the security of the lithium battery that uses present lithium-cobalt system composite oxides, lithium-nickel-based compound oxide or lithium manganese system complex oxide.At this moment, and the physicals of the lithium-cobalt system composite oxides of usefulness, lithium-nickel-based compound oxide or lithium manganese system complex oxide etc. has no particular limits, but median size is 1.0～20 μ m, be preferably 1.0～15 μ m, 2.0～10 μ m more preferably, and the BET specific surface area is 0.1～2.0m 2/ g, be preferably 0.2～1.5m 2/ g, 0.3～1.0m more preferably 2/ g.
[embodiment]
Below, illustrate in greater detail the present invention according to embodiment, but the present invention is not subjected to the restriction of these embodiment.
＜ferrous sulfate heptahydrate (FeSO 47H 2O) 〉
The ferrous heptahydrate of the raw material sulphuric acid of Shi Yonging uses commercially available industrial goods in an embodiment, and its grade is shown in Table 1.
Obtain the content of Na, Ti, Mn, Zn, Cr, Ni, Cu, Co with the ICP optical spectroscopy.
Table 1
The foreign matter content of ferrous sulfate heptahydrate
Na content (ppm) 13
Ti content (ppm) 1200
Mn content (ppm) 3900
Zn content (ppm) 96
Co content (ppm) 29
Cr content (ppm) 4
Ni content (ppm) 18
Cu content (ppm) Below 1
Synthesizing of＜ferrous phosphate hydrated salt crystal 〉
Embodiment 1
In 3L water, dissolve the ferrous sulfate heptahydrate (FeSO of 907g (3mol) 47H 2O) and the 75% phosphoric acid (H of 26lg (2mol) 3PO 4), make mixing solutions (17 ℃ of temperature, pH1.6).With the speed of dripping of 83ml/min, with 16% sodium hydroxide (NaOH) aqueous solution of the 1500ml (6mol) that drips in 18 fens these mixing solutionss of clockwise, make ferrous phosphate separate out (31 ℃ of temperature, pH6.7).
Then, carry out the filtered and recycled ferrous phosphate, the ferrous phosphate that reclaims is carefully cleaned with 4.5L water.
Then, dry 23 hours of the ferrous phosphate after will cleaning under 50 ℃ of temperature obtains the 490g dry product.With the resulting dry product of X-ray diffraction analysis, its result, diffractogram is consistent with JCPDS (JCPDS) figure number 30-662, therefore confirms that dry product is Fe 3(PO 4) 28H 2O (yield 98%).
At resulting Fe shown in the table 2 3(PO 4) 28H 2All physicalies of O.
In addition, use CuK α line as radioactive source to resulting Fe 3(PO 4) 28H 2O carries out X-ray diffraction analysis, measures near the half breadth of the diffraction peak (020 face) 2 θ=13.1 °, and it the results are shown in the table 2.In addition, resulting Fe shown in Figure 1 3(PO 4) 28H 2The X-ray diffractogram of O.
Utilize the ICP optical spectroscopy to obtain the content of Na, Ti, Mn, Zn, Cr, Ni, Cu, Co.In addition, thus will convert by the S atomic percent measurement result that the ICP optical spectroscopy records and obtain SO 4Content utilizes absorption photometry to obtain the P content of this dry product.The high person of this P content value represents the purity height of dry product.In addition, utilize laser diffractometry to obtain median size.
Embodiment 2
In 3L water, dissolve the ferrous sulfate heptahydrate (FeSO of 816g (2.7mol) 47H 2O) and the 75% phosphoric acid (H of 261g (2mol) 3PO 4), make mixing solutions (8 ℃ of temperature, pH0.6).With the speed of dripping of 166ml/min, with 24% sodium hydroxide (NaOH) aqueous solution of the 1000ml (6mol) that drips in 6 fens these mixing solutionss of clockwise, make ferrous phosphate separate out (21 ℃ of temperature, pH7.4).
Then, carry out the filtered and recycled ferrous phosphate, the ferrous phosphate that reclaims is carefully cleaned with 4.5L water.
Then, dry 23 hours of the ferrous phosphate after will cleaning under 50 ℃ of temperature obtains the 480g dry product.With the dry product that X-ray diffraction analysis obtains, its result, diffractogram is consistent with JCPDS (JCPDS) figure number 30-662, therefore confirms that dry product is Fe 3(PO 4) 28H 2O (yield 94%).
At resulting Fe shown in the table 2 3(PO 4) 28H 2All physicalies of O.
And, utilize the method identical to obtain Na, Ti, Mn, Zn, Cr, Ni, Cu, Co, SO with embodiment 1 4Content, P content and median size.
Comparative example 1
In 1L water, dissolve the ferrous sulfate heptahydrate (FeSO of 278g (1mol) 47H 2O), make the ferrous phosphate aqueous solution.In 2L water, dissolve the sodium hydrogen phosphate dodecahydrate (Na of 240g (0.67mol) in addition 2HPO 412H 2O), make the sodium hydrogen phosphate aqueous solution.With the speed of dripping of 56ml/min, with the 36 fens sodium hydrogen phosphate aqueous solution that drips in the clockwise ferrous phosphate aqueous solution, ferrous phosphate is separated out.
Then, carry out the filtered and recycled ferrous phosphate, the ferrous phosphate that reclaims is carefully cleaned with 4.5L water.
Then, dry 23 hours of the ferrous phosphate after will cleaning under 45 ℃ of temperature obtains the 82g dry product.With the dry product that X-ray diffraction analysis obtains, its result, diffractogram is consistent with JCPDS (JCPDS) figure number 30-662, therefore confirms that dry product is Fe 3(PO 4) 28H 2O (yield 49%).
At resulting Fe shown in the table 2 3(PO 4) 28H 2All physicalies of O.
In addition, use CuK α line as radioactive source to resulting Fe 3(PO 4) 28H 2O carries out X-ray diffraction analysis, measures near the half breadth of the diffraction peak (020 face) 2 θ=13.1 °, X-ray diffractogram shown in Figure 2.
And, utilize the method identical to obtain Na, Ti, Mn, Zn, Cr, Ni, Cu, Co, SO with embodiment 1 4Content, P content and median size.
Comparative example 2
With embodiment 1 in the same manner to commercially available ferrous phosphate (Fe 3(PO 4) 28H 2O) carry out X-ray diffraction analysis, measure near diffraction peak half breadth, Na, Ti, Mn, Zn, Cr, Ni, Cu, Co and the SO of the lattice plane (020 face) 2 θ=13.1 ° 4Content, P content and median size, it the results are shown in the table 2.
Table 2
Embodiment 1 Embodiment 2 Comparative example 1 Comparative example 2
P content (weight %) 12.2 12.2 12.2 12.2
Median size (μ m) 2.3 4.6 17.9 7.1
The half breadth of (020 face) (°) 0.34 0.22 0.19 0.14
Na content (weight %) 0.433 0.550 0.560 0.120
SO 4Content (weight %) 0.596 0.580 0.617 0.340
Ti content (weight %) 0.278 0.170 0.313 -
Mn content (weight %) 0.579 0.670 0.679 0.0832
Zn content (weight %) 0.018 0.014 0.019 0.0045
Co content (weight %) 0.005 0.006 0.007 0.0006
Cr content (weight %) 0.001 0.001 0.001 0.0044
Ni content (weight %) 0.003 - 0.003 0.0046
Cu content (weight %) 0.001 0.002 0.002 -
Notes) "-" expression limit of detection in the table is below the 1ppm.
Synthesizing of＜ithium iron phosphorus series composite oxides 〉
Embodiment 3
Utilize Henschel mixer with the ferrous phosphate hydrated salt crystal (Fe that is modulated among the 10kg embodiment 1 3(PO 4) 28H 2O), 2.4kg Trilithium phosphate (Li 3PO 4, median size 5.8 μ m, FMC society system) and the 1kg particle diameter be that the high conductivity carbon black (ケ Star チ エ Application Block ラ Star Network イ Application one Na シ ヨ Na Le society system, trade(brand)name ECP) of 0.05 μ m mixes fully.Then, use dry type bead grinding mechanism that this mixture is carried out pulverization process, obtain reacting elementary thing.Main physical performance at the elementary thing of resulting reaction shown in the table 3.
In addition, in the graduated cylinder of 50ml, put into the 10g sample, be fixed on dual automatic jolt ramming (DUAL AUTOTAP) device of " YUASA-IONICS (strain) " system, after the jolt ramming 500 times, read volume, obtain the specific volume of bead grinding machine pulverizing product according to following formula.
[mathematical expression 2]
Specific volume (ml)=V/F
(in the formula, F represents the interior sample mass of handling (g) of receiver, and V represents the sample volume (ml) after the jolt ramming.)
The condition of dry type bead grinding mechanism is as follows.
Circulating medium thing: alumina beads (median size is 5mm)
Spatial volume: 64%
Circumferential speed: 5.2m/s
Then, the pulverizing product that obtain under nitrogen atmosphere, carry out firing in 5 hours at 600 ℃, after the cooling, are pulverized, classification, obtained coating the LiFePO of high conductivity carbon black 4At the LiFePO that coats the high conductivity carbon black shown in the table 4 4The Main physical performance.
Utilize the ICP optical spectroscopy to obtain the content of Na, Ti, Mn, Zn, Cr, Ni, Cu, Co.In addition, the S atomic percent measurement result of utilizing the ICP optical spectroscopy to measure is converted obtain SO 4Content.Utilize electron micrograph to obtain median size.In addition, (society of Shimadzu Seisakusho Ltd. system TOC-5000A) is measured the LiFePO that has coated the high conductivity carbon black to utilize full organic body carbon element meter 4In the C atom content.
Embodiment 4
Utilize Henschel mixer with the phosphoric acid industry iron hydrated salt crystal (Fe that is modulated among the 10kg embodiment 1 3(PO 4) 28H 2O), 2.4kg Trilithium phosphate (Li 3PO 4, median size 5.8 μ m, FMC society system) and the 1kg particle diameter be that the high conductivity carbon black (ケ Star チ エ Application Block ラ Star Network イ Application one Na シ ヨ Na Le society system, trade(brand)name ECP) of 0.1 μ m mixes fully.Then, use dry type bead grinding mechanism that this mixture is carried out pulverization process, obtain reacting elementary thing.Measure the Main physical performance of the elementary thing of resulting reaction in the same manner with embodiment 3, it the results are shown in the table 3.The condition of dry type bead grinding mechanism is as follows.
Circulating medium thing: alumina beads (median size is 5mm)
Spatial volume: 75%
Circumferential speed: 5.2m/s
Then, use hand press, with 44MPa 10g is reacted elementary thing and is pressed.Then, these compression moulding product under nitrogen atmosphere, carry out firing in 5 hours at 600 ℃, after the cooling, are pulverized, classification, obtained coating the LiFePO of high conductivity carbon black 4Obtain median size, BET specific surface area, Na, Ti, Mn, Zn, Cr, Ni, Cu, Co, the SO of resulting ithium iron phosphorus series complex body with the method identical with embodiment 3 4, the C atom content.It the results are shown in the table 4.And the X-ray diffraction of the ithium iron phosphorus series composite oxides that make is illustrated among Fig. 3.
Embodiment 5
Utilize Henschel mixer with the ferrous phosphate hydrated salt crystal (Fe that is modulated among the 10kg embodiment 1 3(PO 4) 28H 2O), 2.4kg Trilithium phosphate (Li 3PO 4, median size 5.8 μ m, FMC society system) and the 1kg particle diameter be that the high conductivity carbon black (ケ Star チ エ Application Block ラ Star Network イ Application one Na シ ヨ Na Le society system, trade(brand)name ECP) of 0.1 μ m mixes fully.Then, use dry type bead grinding mechanism that this mixture is carried out pulverization process, obtain reacting elementary thing.Measure the Main physical performance of the elementary thing of resulting reaction in the same manner with embodiment 3, it the results are shown in the table 3.
The condition of dry type bead grinding mechanism is as follows.
Circulating medium thing: alumina beads (median size is 8mm)
Spatial volume: 75%
Circumferential speed: 4.7m/s
Then, use hand press, with 44MPa 10g is reacted elementary thing and is pressed.Then, these compression moulding product under nitrogen atmosphere, carry out firing in 5 hours at 600 ℃, after the cooling, are pulverized, classification, obtained coating the LiFePO of high conductivity carbon black 4Obtain median size, BET specific surface area, Na, Ti, Mn, Zn, Cr, Ni, Cu, Co, the SO of resulting ithium iron phosphorus series complex body with the method identical with embodiment 3 4, the C atom content.It the results are shown in the table 4.
Embodiment 6
Synthesizing of＜manganous phosphate 〉
In 25L water, dissolve 1352g (8mol) manganous sulfate monohydrate (MnSO 4H 2O) and the 75% phosphoric acid (H of 697g (5.3mol) 3PO 4), make mixing solutions (pH1.3).With the speed of dripping of 161ml/min, with 4% sodium hydroxide (NaOH) aqueous solution of the 16L (16mol) that drips in 100 fens these mixing solutionss of clockwise, make manganous phosphate separate out (pH6.5).
Then, filter, reclaim manganous phosphate, carefully the manganous phosphate that reclaims is cleaned with 40L water.
Then, the manganous phosphate after cleaning is carried out 23 hours dryings under 50 ℃ of temperature, obtain the 1214g dry product.With the resulting dry product of X-ray diffraction analysis, its result, face interval and diffracted intensity and document (Russ.J.Inorg.Chem. 23, 341,1978) and the data consistent of record, and Mn content is 34.8 weight %, PO 4Content is 40.2 weight %, therefore confirms that this dry product is Mn 3(PO 4) 26H 2O (yield 98%).Have again, resulting manganous phosphate, the median size of being obtained by laser diffractometry is 4.9 μ m.
Synthesizing of＜phosphoric acid (iron-manganese) phosphorus-based complex oxide 〉
Use mixing machine with synthetic ferrous phosphate hydrated salt crystal (Fe among the 23.7g embodiment 1 3(PO 4) 28H 2O), the above-mentioned synthetic manganous phosphate of 25.1g hydrated salt crystal (Mn 3(PO 4) 26H 2O), 12.0g Trilithium phosphate (Li 3PO 4, median size 5.8 μ m, FMC society system) and the 4.9g particle diameter be that the high conductivity carbon black (ケ Star チ エ Application Block ラ ッ Network イ Application one Na シ ヨ Na Le society system, trade(brand)name ECP) of 0.1 μ m mixes fully.Then, use vibrating mill that this mixture is carried out pulverization process, obtain reacting elementary thing.Measure all physicalies of the elementary thing of resulting reaction in the same manner with embodiment 3, be shown in Table 3.
The operating condition of vibrating mill is as follows.
Vibration number: 1000Hz
Treatment time: 3 minutes
The Intake Quantity of raw material: 12g
Then, use hand press, with 44MPa 10g is reacted elementary thing and is pressed.Then, these compression moulding product under nitrogen atmosphere, carry out firing in 5 hours at 600 ℃, after the cooling, are pulverized, classification, obtained coating phosphoric acid (iron-manganese) phosphorus-based complex oxide of high conductivity carbon black.Obtain median size, BET specific surface area, Na, Ti, Mn, Zn, Cr, Ni, Cu, Co, the SO of resulting phosphoric acid (iron-manganese) phosphorus-based complex oxide with the method identical with embodiment 3 4Content.It the results are shown in the table 4.
Table 3
Specific volume (ml/g)
Embodiment 3 1.40
Embodiment 4 1.35
Embodiment 5 1.42
Embodiment 6 1.10
Table 4
Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Median size (μ m) 0.2 0.2 0.2 0.2
BET specific surface area (m 2/g) 57 57 59 59
C atom content (weight %) 8.1 8.1 8.1 8.1
Na content (weight %) 0.29 0.29 0.30 0.31
SO 4Content (weight %) 0.15 0.16 0.15 0.22
Ti content (weight %) 0.12 0.11 0.12 0.07
Mn content (weight %) 0.61 0.60 0.61 18.0
Zn content (weight %) 0.014 0.015 0.014 0.01
Co content (weight %) 0.002 0.003 0.002 0.02
Cr content (weight %) 0.001 0.002 0.001 ＜0.001
Ni content (weight %) 0.002 0.002 0.003 0.01
Cu content (weight %) 0.001 0.001 0.001 ＜0.001
Notes) the C atom content in the table 4 is represented relative LiFePO 4Or LiFe 0.5Mn 0.5PO 4The amount of C atom.
＜reference example 〉
＜battery performance test 〉
(I) making of lithium battery
With the LiFePO that coats as the high conductivity carbon black of the above-mentioned embodiment that makes 3～5 4Carry out vacuum-drying, make the LiFePO utilize this high conductivity carbon black of coating that the Ka Er Karl Fischer titration tries to achieve with 250 ℃ of moisture gasifications 4Moisture content reach below the 1500ppm respectively, mix these ithium iron phosphorus series composite oxides of 91 weight %, the powdered graphite of 6 weight % and the polyvinylidene dichloride of 3 weight %, as positive pole, it is dissolved in the N-N-methyl-2-2-pyrrolidone N-, be modulated into mixing cream.After should mixing cream being coated on the aluminium foil, carry out punching press, strike out the disk that diameter is 15mm, obtain positive plate.
Use this positive plate, re-use each parts such as barrier film, negative pole, positive pole, collector electrode, mounted apparatus, outside terminal, electrolytic solution, make lithium battery.Wherein, negative pole uses metallic lithium foil, concerning electrolytic solution, uses 1 mole of LiPF of dissolving in 1: 1 mixing liquid of 1L ethylene carbonate and Methyl ethyl carbonate 6Solution.
(II) performance evaluation of battery
The lithium battery of making is at room temperature worked, the discharge capacity after mensuration initial stage discharge capacity and 10 circulations.In addition, calculate LiFePO according to following formula 4The ratio of theoretical discharge capacity (170mAh/g).
[mathematical expression 3]
Table 5
Initial stage discharge capacity (mAh/g) Discharge capacity (mAh/g) after 10 circulations Ratio (%) to theoretical discharge capacity
Embodiment 3 150 158 93
Embodiment 4 151 159 94
Embodiment 5 151 161 95
As can be known from the results of Table 5, the LiFePO to use ferrous phosphate hydrated salt crystal of the present invention to make 4Lithium battery as positive active material demonstrates near LiFePO 4The value of theoretical discharge capacity, obtain the lithium battery of high discharge capacity.
(effect of invention)
As mentioned above, ferrous phosphate hydrated salt crystal of the present invention is adaptive functions inorganic material, the special LiFePO that uses as the positive active material of lithium storage battery4Perhaps LiFeMePO4The ferrous phosphate hydrated salt crystal fine and that crystallinity is low of the manufacturing raw material purposes of (Me represents to be selected from least a among Mn, Co, Ni, the Al or more than one metallic element). In addition, manufacturing method according to the invention can be with high yield at industrial this ferrous phosphate hydrated salt crystal of advantageously making. In addition, with ferrous phosphate hydrated salt crystal of the present invention as make raw material, to use ithium iron phosphorus series composite oxides that this manufacturing raw material obtains as the lithium storage battery of positive active material, demonstrate near LiFePO4The value of theoretical discharge capacity.

Claims (18)

1. ferrous phosphate hydrated salt crystal is with general formula Fe 3(PO 4) 28H 2O represents, it is characterized in that: median size is below the 5 μ m.
2. ferrous phosphate hydrated salt crystal according to claim 1 is characterized in that: the half breadth of the diffraction peak of the lattice plane of being obtained by X-ray diffraction analysis (020 face) is more than 0.20 °.
3. ferrous phosphate hydrated salt crystal according to claim 1 is characterized in that: the content as the Na of impurity is below the 1 weight %.
4. ferrous phosphate hydrated salt crystal according to claim 2 is characterized in that: the content as the Na of impurity is below the 1 weight %.
5. the manufacture method of a ferrous phosphate hydrated salt crystal is characterized in that: add alkali and react in the aqueous solution that contains divalent iron salt and phosphoric acid.
6. the manufacture method of ferrous phosphate hydrated salt crystal according to claim 5 is characterized in that: described divalent iron salt is the ferrous sulfate heptahydrate.
7. the manufacture method of ithium iron phosphorus series composite oxides is characterized in that: each described ferrous phosphate hydrated salt crystal, Trilithium phosphate and conductive carbon material in the claim 1 to 4 are mixed, and fire.
8. the manufacture method of ithium iron phosphorus series composite oxides, it is characterized in that: with each described ferrous phosphate hydrated salt crystal, Trilithium phosphate in the claim 1 to 4, contain at least a of the metallic element that is selected among Mn, Co, Ni and the Al or more than one metallic compound and conductive carbon material mix, and fire.
9. the manufacture method of ithium iron phosphorus series composite oxides according to claim 7 is characterized in that: comprising: with each described ferrous phosphate hydrated salt crystal, Trilithium phosphate and conductive carbon material blended first operation in the claim 1 to 4; Then, thus with drying process resulting mixture is carried out second operation that pulverization process obtains reacting elementary thing; Then, thus fire this and react the 3rd operation that elementary thing obtains the ithium iron phosphorus series composite oxides.
10. the manufacture method of ithium iron phosphorus series composite oxides according to claim 8 is characterized in that: comprising: with each described ferrous phosphate hydrated salt crystal, Trilithium phosphate in the claim 1 to 4, contain at least a of the metallic element that is selected among Mn, Co, Ni and the Al or more than one metallic compound and conductive carbon material blended first operation; Then, thus with drying process resulting mixture is carried out second operation that pulverization process obtains reacting elementary thing; Then, thus fire this and react the 3rd operation that elementary thing obtains the ithium iron phosphorus series composite oxides.
11. the manufacture method of ithium iron phosphorus series composite oxides according to claim 9 is characterized in that: after described second operation, the operation that the elementary thing of resulting reaction is carried out extrusion forming is set.
12. the manufacture method of ithium iron phosphorus series composite oxides according to claim 10 is characterized in that: after described second operation, the operation that the elementary thing of resulting reaction is carried out extrusion forming is set.
13. the manufacture method of ithium iron phosphorus series composite oxides according to claim 7 is characterized in that: the median size of the ithium iron phosphorus series composite oxides that generated is below the 0.5 μ m.
14. the manufacture method of ithium iron phosphorus series composite oxides according to claim 8 is characterized in that: the median size of the ithium iron phosphorus series composite oxides that generated is below the 0.5 μ m.
15. the manufacture method of ithium iron phosphorus series composite oxides according to claim 9 is characterized in that: the median size of the ithium iron phosphorus series composite oxides that generated is below the 0.5 μ m.
16. the manufacture method of ithium iron phosphorus series composite oxides according to claim 10 is characterized in that: the median size of the ithium iron phosphorus series composite oxides that generated is below the 0.5 μ m.
17. the manufacture method of ithium iron phosphorus series composite oxides according to claim 11 is characterized in that: the median size of the ithium iron phosphorus series composite oxides that generated is below the 0.5 μ m.
18. the manufacture method of ithium iron phosphorus series composite oxides according to claim 12 is characterized in that: the median size of the ithium iron phosphorus series composite oxides that generated is below the 0.5 μ m.
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