CN104269528B - A kind of preparation method of cobalt phosphate powder body material - Google Patents
A kind of preparation method of cobalt phosphate powder body material Download PDFInfo
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- CN104269528B CN104269528B CN201410453227.1A CN201410453227A CN104269528B CN 104269528 B CN104269528 B CN 104269528B CN 201410453227 A CN201410453227 A CN 201410453227A CN 104269528 B CN104269528 B CN 104269528B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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
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Abstract
The invention discloses a kind of preparation method of cobalt phosphate powder body material, by soluble cobalt and soluble phosphoric acid reactant salt are precipitated after thing C.I. Pigment Violet 14, reaction system is adjusted to neutrality with ammonia, then by reaction system sucking filtration, washing, it is dried, grinding, cobalt phosphate powder body material is obtained after screening, preparation method provided by the present invention is simple, it is easy to operate, low cost, and the impurity content in the product cobalt phosphate powder body material of gained is few, the pattern and granularity of the cobalt phosphate powder body material for being obtained by the preparation technology in addition is controllable, so as to meet the demand of different battery materials.
Description
Technical field
The present invention relates to lithium ion secondary positive electrode field, more particularly to a kind of preparation side of cobalt phosphate powder body material
Method.
Background technology
Since successfully developing lithium ion battery from Sony corporation of Japan in 1991, develop through more than 20 years, lithium ion
Battery has been widely used in every field, such as 3C electronic products, electric motor car, energy storage etc..
Lithium ion battery is the green high-capacity battery of a new generation, because with spies such as energy height, long service life, low stains
Point, wherein, positive electrode is the important component part of lithium ion battery, in occupation of most important in lithium ion battery structure
Position, the quality of its performance directly determines the performance of final secondary cell product, and its performance and price can be directly influenced
The performance and price of lithium rechargeable battery.
With the upgrading of product, product manufacturing manufacturer requires more and more higher to the energy density of lithium ion battery.It is logical
Cross and adopt high-voltage anode material, such as LiNi0.5Mn1.5O4、LiCoPO4、LiMnPO4、LiNiPO4Deng, can significantly improve lithium from
Sub- battery energy density.Wherein, work as LiCoPO4During the positive electrode used as lithium ion battery, theoretical capacity is 167mAh/
G, is 4.8v～4.9v, and LiCoPO to lithium electrode current potential4Crystal there is orderly olivine-type structure, belong to orthorhombic
System, has a safety feature, is expected to become high power capacity of new generation, high voltage, the positive electrode of high safety.
The performance of the raw material C.I. Pigment Violet 14 of synthesis presoma to the electrical property such as charge/discharge capacity of anode material for lithium-ion batteries,
Cycle life, processing characteristics etc. have a major impact.It should be particularly mentioned that, lithium battery grade C.I. Pigment Violet 14 except require strict chemistry into
Exceptionally, also there are strict requirements to physical indexs such as particle size distribution, but through investigation, with regard to the side of the synthetic method of C.I. Pigment Violet 14
The particularss in face are less, also lack the research data to granularity and morphology control.
At present, common C.I. Pigment Violet 14 mainly has following two synthetic methods：
One kind is that soluble cobalt generates C.I. Pigment Violet 14 precipitation with phosphate reaction, and the method is although with low cost, but miscellaneous
Matter content is high；
Another kind is that the hydrate and water of pyrophosphoric acid cobalt are placed in seal pipe to be heated to 250 DEG C so as to prepare, and is lacked
Point is low yield, high cost.
The content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, as a result find：By by soluble cobalt and can
After soluble phosphoric acid reactant salt is precipitated thing C.I. Pigment Violet 14, reaction system is adjusted to neutrality with ammonia, then reaction system is taken out
Filter, washing are dried, and grinding obtains cobalt phosphate powder body material, so as to complete the present invention after screening.
It is an object of the invention to provide a kind of preparation method of cobalt phosphate powder body material, the method is comprised the following steps：
1) soluble cobalt is added in the water of container I, is configured to water solution A, soluble phosphate is added to into appearance
In the water of device II, aqueous solution B is configured to, wherein,
The soluble cobalt is cobaltous chloride, cobalt nitrate, one or more in cobaltous sulfate,
The soluble phosphate is ammonium dihydrogen phosphate, diammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, di(2-ethylhexyl)phosphate
One or more in hydrogen potassium, dipotassium hydrogen phosphate；
2) the aqueous solution B in container II is added in the water solution A in container I, under 20～80 DEG C of temperature conditionss
Reaction, after the completion of reaction, reaction temperature is constant, and ammonification water adjusts reaction system so that reaction system is in neutrality, wherein,
The addition of the aqueous solution B is the cobalt element in mole and the water solution A for cause the phosphate radical in aqueous solution B
Mole ratio be PO4 3-：Co=2:3；
3) by step 2) in the reaction system that obtains obtain phosphoric acid cobalt powder after sucking filtration, washing, drying, grinding, screening
Body material, wherein, washed with water.
Another object of the present invention is to provide the cobaltous sulfate powder body material that a kind of preparation method provided by the present invention is obtained
Material, wherein,
The meso-position radius of the C.I. Pigment Violet 14 be 1～25 micron, in C.I. Pigment Violet 14 the content of sodium element be 0～100ppm, magnesium elements
Content be 0～100ppm, the content of calcium constituent is 0～100ppm.
It is still another object of the present invention to provide the C.I. Pigment Violet 14 that a kind of preparation method provided by the present invention is obtained is used to make
Standby anode material for lithium-ion batteries LiCoPO4Purposes.
A kind of preparation method of C.I. Pigment Violet 14 positive electrode that the present invention is provided, the preparation process is simple, easy to operate, cost
It is low, it is suitable to large-scale industrialization production, it is even more important that the impurity content in the product C.I. Pigment Violet 14 obtained by the method
It is low, can apply in anode material for lithium-ion batteries LiCoPO as raw material4Preparation in such that it is able to improve positive electrode
Charge/discharge capacity, cycle life, processing characteristics, in addition, the pattern and grain of the cobalt phosphate powder body material obtained by the preparation technology
Degree is controllable, so as to meet the demand of different battery materials.
Description of the drawings
Fig. 1 illustrates the scanning electron microscope (SEM) photograph of the cobalt phosphate powder body material by obtained by embodiment 1；
Fig. 2 illustrates the scanning electron microscope (SEM) photograph of the cobalt phosphate powder body material by obtained by embodiment 3；
Fig. 3 illustrates the particle size distribution figure of the cobalt phosphate powder body material by obtained by embodiment 1；
Fig. 4 illustrates the particle size distribution figure of the cobalt phosphate powder body material by obtained by embodiment 3；
Fig. 5 illustrates the scanning electron microscope (SEM) photograph of the cobalt phosphate powder body material in comparative example 2；
Fig. 6 illustrates the particle size distribution figure of the cobalt phosphate powder body material in comparative example 2.
Specific embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
For clear, clear and definite.
According to an aspect of the present invention, there is provided a kind of preparation method of cobalt phosphate powder body material, the method includes following
Three steps：
Step one, soluble cobalt is added in the water of container I, is configured to water solution A, soluble phosphate is added
To in the water of container II, aqueous solution B is configured to.
In above-mentioned steps one, soluble cobalt is cobaltous chloride, cobalt nitrate, one or more in cobaltous sulfate.
Wherein, the chemical formula of cobaltous chloride is specifically referred to：CoCl2And CoCl26H2O；The chemical formula of cobalt nitrate is specifically referred to：Co
(NO3)2·6H2O；The chemical formula of cobaltous sulfate is specifically referred to：CoSO4·7H2O。
A kind of in above-mentioned steps, the phosphate of solubility is ammonium dihydrogen phosphate, diammonium phosphate, sodium dihydrogen phosphate, phosphoric acid
One or more in disodium hydrogen, potassium dihydrogen phosphate, dipotassium hydrogen phosphate.
In a preferred embodiment, the phosphate of solubility be ammonium dihydrogen phosphate, the one kind or many in diammonium hydrogen phosphate
Kind, select above-mentioned ammonium dihydrogen phosphate and diammonium hydrogen phosphate to react with soluble cobalt, due to the aminated compoundss for generating be easy to by
Remove, hence in so that the impurity content in the C.I. Pigment Violet 14 for finally giving is few.
In above-mentioned steps one, soluble cobalt is substantially dissolved in water, is configured to the water solution A of stable homogeneous, wherein,
The concentration of water solution A is 0.017～8.5mol/L, and especially, the concentration of water solution A is 0.1～5mol/L, further, water
The concentration of solution A is preferably 0.2～3mol/L, and further, the concentration of water solution A is preferably 0.3～2mol/L.
In above-mentioned steps one, soluble phosphate is substantially dissolved in water, is configured to the aqueous solution B of stable homogeneous, its
In, the concentration of aqueous solution B is 0.017～9.0mol/L, and especially, the concentration of aqueous solution B is 0.1～5mol/L, further,
The concentration of aqueous solution B is preferably 0.2～3mol/L, and further, the concentration of aqueous solution B is preferably 0.25～2mol/L.
In above-mentioned steps one, water be tap water, mineral water, distilled water, one or more in deionized water, especially
Ground, preferred deionized water.
Step 2, the aqueous solution B in container II is added in the water solution A in container I, under conditions of 20～80 DEG C
Reaction, after the completion of reaction, reaction temperature is constant, and ammonification water adjusts reaction system so that reaction system is in neutrality.
In a preferred embodiment, aqueous solution B uniformly continuous are added in water solution A, especially, aqueous solution B with
The speed of 0.5～20ml/min is added in water solution A, further, preferably 1～15ml/min, and further, preferably 2
～10ml/min, most preferably 2.5～5ml/min.
In above-mentioned steps two, under 20～80 DEG C of reaction condition, aqueous solution B is added in water solution A, Liang Zheneng
Enough fast reactions, if reaction temperature is less than 20 DEG C, due to reaction temperature it is too low so that water solution A and aqueous solution B can not be quick
Effectively react, so as to affect production efficiency, additionally, being unfavorable for growing up for the nucleus of the product for finally giving, obtain
Particle size is too small, therefore lattice defect is more；If reaction temperature be higher than 80 DEG C, due to temperature it is too high so that response speed
It is too fast, the control for producing is not easy to, additionally, can also affect the particle diameter distribution of final product so that particle diameter distribution is uneven.
Especially, reaction temperature is 25～70 DEG C, and further, reaction temperature is preferably 25～60 DEG C.
In above-mentioned steps two, the addition of aqueous solution B causes the mole and water solution A of the phosphate radical in aqueous solution B
In cobalt element mole ratio be PO4 3-：Co=2:3.
In above-mentioned steps two, when aqueous solution B is added in water solution A, reaction stir speed (S.S.) is 50～500rpm, special
Not, preferably 80～400rpm, further, stir speed (S.S.) preferably 100～300rpm, further, stir speed (S.S.) is preferred
100～200rpm.
In above-mentioned steps two, after reaction terminates, temperature conditionss are constant, and addition ammonia causes the pH value of reaction system into
Property, especially, reaction stir speed (S.S.) is constant, after continuing stirring 0.1h～1h, finally gives mixed material.
After completion of the reaction, as reaction system is in acidity, add ammonia so that reaction system is in neutrality, so that
Final product stable existence, if final product is present in acid reaction system, can cause the dissolving of final product, so as to make
Into the loss of yield of final product.
In above-mentioned steps two, the concentration of ammonia is not especially limited, as long as can adjust the pH value of reaction system
To neutral, especially, the pure ammonia of analysis that mass percent concentration is 25% is selected.
In above-mentioned steps two, the mode of ammonia is added to be not exposed to especially limit, disposable addition or Deca are equal
Can, in particular it is preferred to Deca ammonia so that ammonia full and uniform can be blended in reaction system.
Step 3, by step 2 through in ammonia and after the reaction system that obtains through sucking filtration, washing, drying, grinding,
Cobalt phosphate powder body material is obtained after sieving.
In above-mentioned steps three, through the reaction system sucking filtration obtained with after in ammonia, pink will be obtained in step 2
Precipitate, is then washed to the precipitate with water, and the number of times of washing is not exposed to especially limit, in order to take into account production effect
Rate and some ions adsorbed on precipitate can be removed as far as possible, preferably wash 1～5 time, more preferably wash 2～3 times.
In above-mentioned steps three, water is preferably deionized water.
Precipitate is washed with water after washing, and precipitate is dried.Wherein, dry mode is not especially limited, can
To dry naturally, it is also possible to dry under uniform temperature again.
Especially, dry 5～30 hours under 80～200 DEG C of temperature conditionss, so as to inhale on disgorging C.I. Pigment Violet 14
Attached moisture.Further, temperature is preferably 100～160 DEG C, and further, temperature is preferably 120～150 DEG C.Especially
Ground, drying time are 10～25 hours, and further, temperature is preferably 15～24 hours.
In above-mentioned steps three, dried precipitate is ground, wherein, the mode of grinding is not exposed to specific limit
System, can according to the actual requirements, and the method for selecting grinding, after grinding, is crossed 300 mesh sieves, especially, obtains peach lamellar
Or spherical C.I. Pigment Violet 14.
According to a further aspect in the invention, there is provided the C.I. Pigment Violet 14 that a kind of method provided by the present invention is prepared is by under
Shown in formula I：
Co3(PO4)2·8H2O
Formula I
Wherein, the meso-position radius (D50) of C.I. Pigment Violet 14 are 1～25 micron, in particular it is preferred to 3～20 microns, it is further, excellent
3～13 microns are selected, and particle diameter is in normal distribution, is evenly distributed.
The C.I. Pigment Violet 14 that preparation method provided by the present invention is obtained, using ethylenediaminetetraacetic acid (EDTA) in C.I. Pigment Violet 14
Co2+Complexometry is carried out, can learn that the percentage by weight of cobalt element in C.I. Pigment Violet 14 is 36.5～38.5% through detection.Thus
The percentage by weight and C.I. Pigment Violet 14 chemical formula of cobalt element in the C.I. Pigment Violet 14 that preparation method provided by the present invention is obtained can be drawn
In cobalt element percentage by weight it is basically identical.
In the C.I. Pigment Violet 14 that preparation method provided by the present invention is obtained, through inductively coupled plasma atom diverging light
After spectrometry (ICP) detection, the content for obtaining sodium element in cobalt phosphate powder body material is 0～100ppm, especially, 0 can be reached～
55ppm, even up to 0～26ppm, further, can reach 0～3ppm；The content of magnesium elements is 0～100ppm, especially
Ground, can reach 0～24ppm, further, can reach 3～24ppm, further, can reach 3～5ppm；Calcium constituent
Content is 0～100ppm, especially, can reach 6～59ppm, further, can reach 6～15ppm, further, can
Reach 6～7ppm.Therefore deduce that, the impurity content in C.I. Pigment Violet 14 is few, the purity of C.I. Pigment Violet 14 is high, so as to improve C.I. Pigment Violet 14
Performance, in particular so that the C.I. Pigment Violet 14 for obtaining can apply the positive electrode in lithium ion battery as a kind of raw material
LiCoPO4Preparation in.
However, it is desirable to explanation, above-mentioned mechanism is only that a kind of probability speculates, the present invention is not limited to this.
In accordance with a further aspect of the present invention, the C.I. Pigment Violet 14 that preparation method provided by the present invention is obtained is used for lithium ion battery
Positive electrode purposes.
Due to the C.I. Pigment Violet 14 that preparation method provided by the present invention is obtained, even particle size distribution, impurity content are few, therefore,
Can apply in the preparation of the presoma of the positive electrode of lithium ion battery as a kind of raw material, such that it is able to lift lithium ion
The charge/discharge capacity of the positive electrode of battery, cycle life and processing characteristics.
Embodiment
The present invention is further described below by way of instantiation.But these examples are only exemplary, not to this
The protection domain of invention constitutes any restriction.
In following embodiments and comparative example, the ammonia homogeneous quality percent concentration is the 25% pure ammonia of analysis
Water.
Embodiment 1
1) weigh 84.0gCoSO4·7H2O is added in the deionized water of the 734mL of container I, is configured to water solution A, is claimed
Take 26.4g (NH4)2HPO4In the deionized water of the 734mL for being added to container II, aqueous solution B is configured to；
2) aqueous solution B is added in water solution A, reaction temperature is 25 DEG C, and stir speed (S.S.) is 200rpm, and reaction is completed
Afterwards, reaction temperature is constant, adds ammonia to adjust reaction system so that reaction system is in neutrality；
3) by the reaction system sucking filtration obtained in step 2, ion-cleaning 2 times is spent, then 24h is dried at 120 DEG C, most
300 mesh sieves are crossed eventually obtains cobalt phosphate powder body material.
Jing Beckman particle size analyzers are measured：The meso-position radius (D50) of the cobalt phosphate powder body material for obtaining are 3.1 microns, D10
For 1.2 microns, D90 is 15.1 microns.
Jing after ICP detections, in cobalt phosphate powder body material, impurity content is as follows：The content of sodium element be 55ppm, magnesium unit
The content of element is 24ppm and the content of calcium constituent is 59ppm.
Through compleximetry, learn that the content of the cobalt element in gained cobalt phosphate powder body material is 36.9wt%.
Scanned Electronic Speculum test, gained cobalt phosphate powder body material is lamellar.
Embodiment 2
1) 87.3gCo (NO are weighed3)2·6H2O is added in the deionized water of the 200mL of container I, is configured to water solution A,
Weigh 26.4g (NH4)2HPO4In the deionized water of the 150mL for being added to container II, aqueous solution B is configured to；
2) aqueous solution B is added in water solution A with the speed of 3ml/min, reaction temperature is 60 DEG C, stir speed (S.S.) is
100rpm, after the completion of reaction, reaction temperature is constant, and Deca ammonia adjusts reaction system so that reaction system adds ammonia in neutrality
After water, continue stirring 0.5h；
3) by the reaction system sucking filtration obtained in step 2, ion-cleaning 3 times is spent, then 24h is dried at 150 DEG C, most
300 mesh sieves are crossed eventually obtains cobalt phosphate powder body material.
Jing Beckman particle size analyzers are measured：The meso-position radius (D50) of the cobalt phosphate powder body material for obtaining are 12.7 microns,
D10 is 5.3 microns, and D90 is 22.3 microns.
Jing after ICP detections, in cobalt phosphate powder body material, impurity content is as follows：The content of sodium element be 3ppm, magnesium elements
Content be the content of 5ppm and calcium constituent be 6ppm.
Through compleximetry, learn that the content of the cobalt element in gained cobalt phosphate powder body material is 37.8wt%.
Scanned Electronic Speculum test, gained cobalt phosphate powder body material is lamellar.
Embodiment 3
1) 87.3gCo (NO are weighed3)2·6H2O is added in the deionized water of the 734mL of container I, is configured to water solution A,
Weigh 26.4g (NH4)2HPO4In the deionized water of the 734mL for being added to container II, aqueous solution B is configured to；
2) aqueous solution B is added in water solution A with the speed of 3ml/min, reaction temperature is 60 DEG C, stir speed (S.S.) is
100rpm, after the completion of reaction, reaction temperature is constant, adds ammonia to adjust reaction system so that reaction system adds ammonia in neutrality
After water, continue stirring 0.5h；
3) by the reaction system sucking filtration obtained in step 2, ion-cleaning 2 times is spent, then 24h is dried at 120 DEG C, most
300 mesh sieves are crossed eventually obtains cobalt phosphate powder body material.
Jing Beckman particle size analyzers are measured：The meso-position radius (D50) of the cobalt phosphate powder body material for obtaining are 20.1 microns,
D10 is 11.7 microns, and D90 is 32.6 microns.
Jing after ICP detections, in cobalt phosphate powder body material, impurity content is as follows：The content of sodium element be 0ppm, magnesium elements
Content be the content of 3ppm and calcium constituent be 6ppm.
Through compleximetry, learn that the content of the cobalt element in gained cobalt phosphate powder body material is 36.7wt%.
Scanned Electronic Speculum test, gained cobalt phosphate powder body material is spherical.
Embodiment 4
1) 87.3gCo (NO are weighed3)2·6H2O is added in the deionized water of the 734mL of container I, is configured to water solution A,
Weigh 26.4g (NH4)2HPO4In the deionized water of the 367mL for being added to container II, aqueous solution B is configured to；
2) aqueous solution B is added in water solution A with the speed of 3ml/min, reaction temperature is 60 DEG C, stir speed (S.S.) is
100rpm, after the completion of reaction, reaction temperature is constant, adds ammonia to adjust reaction system so that reaction system adds ammonia in neutrality
After water, continue stirring 0.5h；
3) by the reaction system sucking filtration obtained in step 2, ion-cleaning 2 times is spent, then 24h is dried at 120 DEG C, most
300 mesh sieves are crossed eventually obtains cobalt phosphate powder body material.
Jing Beckman particle size analyzers are measured：The meso-position radius (D50) of the cobalt phosphate powder body material for obtaining are 12.7 microns,
D10 is 8.5 microns, and D90 is 25.6 microns.
Jing after ICP detections, in cobalt phosphate powder body material, impurity content is as follows：The content of sodium element be 5ppm, magnesium elements
Content be the content of 4ppm and calcium constituent be 7ppm.
Through compleximetry, learn that the content of the cobalt element in gained cobalt phosphate powder body material is 37.5wt%.
Scanned Electronic Speculum test, gained cobalt phosphate powder body material is spherical.
Embodiment 5
1) weigh 84gCoSO4·7H2O is added in the deionized water of the 734mL of container I, is configured to water solution A, is weighed
23.0gNH4H2PO4In the deionized water of the 734mL for being added to container II, aqueous solution B is configured to；
2) aqueous solution B is added in water solution A with the speed of 3ml/min, reaction temperature is 25 DEG C, stir speed (S.S.) is
200rpm, after the completion of reaction, reaction temperature is constant, adds ammonia to adjust reaction system so that reaction system adds ammonia in neutrality
After water, continue stirring 0.5h；
3) by the reaction system sucking filtration obtained in step 2, ion-cleaning 2 times is spent, then 24h is dried at 120 DEG C, most
300 mesh sieves are crossed eventually obtains cobalt phosphate powder body material.
Jing Beckman particle size analyzers are measured：The meso-position radius (D50) of the cobalt phosphate powder body material for obtaining are 5.4 microns, D10
For 1.4 microns, D90 is 16.4 microns.
Jing after ICP detections, in cobalt phosphate powder body material, impurity content is as follows：The content of sodium element be 26ppm, magnesium unit
The content of element is 13ppm and the content of calcium constituent is 22ppm.
Through compleximetry, learn that the content of the cobalt element in gained cobalt phosphate powder body material is 36.5wt%.
Scanned Electronic Speculum test, gained cobalt phosphate powder body material is lamellar.
Embodiment 6
1) 71.1g CoCl are weighed2·6H2O is added in the deionized water of the 200mL of container I, is configured to water solution A, is claimed
Take 23.0gNH4H2PO4In the deionized water of the 150mL for being added to container II, aqueous solution B is configured to；
2) aqueous solution B is added in water solution A with the speed of 3ml/min, reaction temperature is 60 DEG C, stir speed (S.S.) is
100rpm, after the completion of reaction, reaction temperature is constant, adds ammonia to adjust reaction system so that reaction system adds ammonia in neutrality
After water, continue stirring 0.5h；
3) by the reaction system sucking filtration obtained in step 2, ion-cleaning 2 times is spent, then 24h is dried at 120 DEG C, most
300 mesh sieves are crossed eventually obtains cobalt phosphate powder body material.
Jing Beckman particle size analyzers are measured：The meso-position radius (D50) of the cobalt phosphate powder body material for obtaining are 12.6 microns,
D10 is 6.6 microns, and D90 is 23.1 microns.
Jing after ICP detections, in cobalt phosphate powder body material, impurity content is as follows：The content of sodium element be 3ppm, magnesium elements
Content be the content of 10ppm and calcium constituent be 15ppm.
Through compleximetry, learn that the content of the cobalt element in gained cobalt phosphate powder body material is 38.1wt%.
Scanned Electronic Speculum test, gained cobalt phosphate powder body material is spherical.
Comparative example
Comparative example 1
Commercially available cobalt phosphate powder body material.
Jing Beckman particle size analyzers are measured：The meso-position radius (D50) of the cobalt phosphate powder body material for obtaining are 27.6 microns,
D10 is 2.4 microns, and D90 is 116.3 microns.
Jing after ICP detections, in cobalt phosphate powder body material, impurity content is as follows：The content of sodium element be 1043ppm, magnesium
The content of element is 387ppm and the content of calcium constituent is 144ppm.
Test example
Scanning electron microscope analysis
To the cobalt phosphate powder body material in the cobalt phosphate powder body material and comparative example 1 of gained in embodiment 1 and embodiment 3
Electronic microscope photos are scanned, respectively as shown in Figure 1, Figure 2 and shown in Fig. 5, can be known：
The cobalt phosphate powder body material that preparation method provided by the present invention is obtained is lamellar or spherical, and pattern rule is and right
The pattern of the C.I. Pigment Violet 14 material in ratio 1 is simultaneously irregular.
Particle diameter distribution
As cobalt phosphate powder body material and comparative example 1 of the Beckman particle size analyzer to embodiment 1 and obtained by implementing in 3
In cobalt phosphate powder body material carry out particle size distribution test, its particle size distribution as shown in Fig. 3, Fig. 4 and Fig. 6, can be obtained respectively
Know：
The particle diameter of the cobalt phosphate powder body material that preparation method provided by the present invention is obtained is less and even particle size distribution, and
C.I. Pigment Violet 14 material particle size in comparative example 1 is larger and particle size distribution width.
Electrochemical property test
The cobalt phosphate powder body material of gained in embodiment 1 is prepared into cobalt phosphate lithium positive electrode I by the following method
And cobalt phosphate powder body material commercially available in comparative example 1 is prepared into cobalt phosphate lithium positive electrode II by the following method：
10g cobalt phosphate powder body materials are mixed with 2.6g lithium carbonate, is mixed after 4 times, in 650 DEG C of condition with 300 mesh sieves sieve
Lower insulation 12h, then grinding sieve, and prepare cobalt phosphate lithium positive electrode.
Cobalt phosphate lithium positive electrode I and cobalt phosphate lithium positive electrode II obtained by above-mentioned preparation is divided by the following method
Do not carry out testing gram volume and first charge-discharge efficiency, it is as a result as shown in table 1 below：
Using cobalt phosphate lithium positive electrode as positive pole, lithium piece is assembled into button cell as negative pole, electric in 3.0v～5.1v
Pressure is tested,
Table 1
Can be learnt by above-mentioned table 1：The positive electrode being prepared from by the cobalt phosphate powder body material that the present invention is prepared
Gram volume it is higher, first charge-discharge efficiency is high, therefore performance is more excellent.
The present invention is described in detail above in association with specific embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Various equivalencings, modification can be carried out to technical solution of the present invention and embodiments thereof or is improved, these each fall within the present invention
In the range of.Protection scope of the present invention is defined by claims.
Claims (8)
1. a kind of preparation method of cobalt phosphate powder body material, the method are comprised the following steps：
1) soluble cobalt being added in the water of container I, is configured to water solution A, the concentration of the water solution A is 0.017～
8.5mol/L, soluble phosphate is added in the water of container II, is configured to aqueous solution B, and the concentration of the aqueous solution B is
0.017～9.0mol/L, wherein, the soluble cobalt is cobaltous chloride, cobalt nitrate, one or more in cobaltous sulfate, described
Soluble phosphate is ammonium dihydrogen phosphate, one or more in diammonium phosphate；
2) the aqueous solution B in container II is added in the water solution A in container I, is reacted under 20～80 DEG C of temperature conditionss,
After the completion of reaction, reaction temperature is constant, and ammonification water adjusts reaction system so that in neutrality, the ammonia is quality to reaction system
Percent concentration is the 25% pure ammonia of analysis, wherein,
The addition of the aqueous solution B is so that cobalt element in mole and the water solution A of phosphate radical in aqueous solution B rubs
The ratio of your amount is PO4 3-：Co=2:3；
3) by step 2) in the reaction system that obtains obtain C.I. Pigment Violet 14 powder body material after sucking filtration, washing, drying, grinding, screening
Material, wherein, washed with water,
The meso-position radius of the C.I. Pigment Violet 14 powder body are 3～13 microns,
The cobalt phosphate powder body material is lamellar or spherical C.I. Pigment Violet 14 powder body, and the sodium element content in cobalt phosphate powder body material is 0
～55ppm, the content of magnesium elements is 3～24ppm and the content of calcium constituent is 6～59ppm.
2. preparation method according to claim 1, it is characterised in that
The concentration of the water solution A is 0.1～5mol/L,
The concentration of the aqueous solution B is 0.1～5mol/L.
3. preparation method according to claim 2, it is characterised in that
The concentration of the water solution A is 0.2～3mol/L,
The concentration of the aqueous solution B is 0.2～3mol/L.
4. preparation method according to claim 3, it is characterised in that
The concentration of the water solution A is 0.3～2mol/L,
The concentration of the aqueous solution B is 0.25～2mol/L.
5. preparation method according to claim 1, it is characterised in that in the step 2) in,
It is 0.5～20ml/min that aqueous solution B is added to the speed in water solution A, and/or
Reaction temperature is 25～70 DEG C, and/or
Water solution A and aqueous solution B are reacted under conditions of stir speed (S.S.) is 50～500rpm.
6. preparation method according to claim 5, it is characterised in that in the step 2) in,
It is 2.5～5ml/min that aqueous solution B is added to the speed in water solution A, and/or
Reaction temperature is 25～60 DEG C, and/or
Water solution A and aqueous solution B are reacted under conditions of stir speed (S.S.) is 100～200rpm.
7. preparation method according to claim 1, it is characterised in that in the step 3) in,
By step 2) in gained reaction system sucking filtration after, be washed with deionized 1～5 time, and/or
After washing, dry 5～30 hours at a temperature of 80～200 DEG C, and/or
After drying, then grinding is crossed 300 mesh sieves and is sieved.
8. preparation method according to claim 7, it is characterised in that in the step 3) in,
By step 2) in gained reaction system sucking filtration after, be washed with deionized 2～3 times, and/or
After washing, dry 5～30 hours at a temperature of 120～150 DEG C.
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