CN103413918A - Synthetic method for cathode material lithium cobaltous phosphate used for lithium ion batteries - Google Patents
Synthetic method for cathode material lithium cobaltous phosphate used for lithium ion batteries Download PDFInfo
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Abstract
The invention discloses a synthetic method for a cathode material lithium cobaltous phosphate used for lithium ion batteries. The method comprises a step of dissolving cobaltous acetate in deionized water to prepare an aqueous solution of the cobaltous acetate; a step of dissolving lithium hydroxide and sucrose in deionized water to prepare a lithium hydroxide/sucrose mixed solution; a step of adding phosphoric acid in deionized water to prepare a phosphoric acid solution; a step of adding the phosphoric acid solution into the aqueous solution of the cobaltous acetate to obtain a burgundy emulsion, stirring uniformly, adding the lithium hydroxide/sucrose mixed solution into the burgundy emulsion, mixing uniformly, and adding nitric acid to obtain a precursor solution; a step of subjecting the precursor solution under stirring to spray drying to obtain a precursor of lithium cobaltous phosphate powder; and a step of subjecting the precursor of the lithium cobaltous phosphate powder to vacuum calcination at 600-750 DEG C for 16-26 h to obtain the cathode material lithium cobaltous phosphate with a spherical porous structure and a high specific capacity.
Description
Technical field
The present invention relates to a kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium material, relate in particular to a kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium material of spherical porous structure.
Background technology
Based on current serious energy crisis and pollution problem, pay much attention to Development of EV countries in the world, in China's 863 Program, also will develop electric motor car and classify the important development direction as.As the research of the electrokinetic cell of vehicle-mounted power, become the Main Bottleneck of power vehicle development.Prevailing battery system is lithium ion battery and nickel-hydrogen cell in the market, and they have replaced nickel-cadmium cell and the lead-acid battery system of transmission gradually.Lithium ion battery because of its high voltage, high power capacity, have extended cycle life and the characteristics such as security performance is good, by extensive concern.
Along with the fast development of lithium ion battery, high power capacity, the anode material for lithium-ion batteries that security performance is good, with low cost become the focus of people's research.A.K.Padhi in 1997 etc. have studied at first and have used the lithium ion battery of the LiMPO4 material of olivine structural as anode material for lithium-ion batteries, find that it has the advantages such as specific capacity that security performance is good, cyclical stability is high, higher, causes many researchers' concern.LiCoPO wherein
4Have orderly olivine-type structure, belong to rhombic system, space group is Pnmb, and cell parameter is a=5.992, b=10.202, c=4.669.At LiCoPO
4In crystal, oxygen atom is close heap hexagonal structure, and what phosphorus atoms occupied is tetrahedral interstice, and what lithium atom and cobalt atom occupied is octahedral interstice.The octahedra CoO of common edge
6On the C direction of principal axis, pass through PO
4Tetrahedron connects into chain structure.This cobalt phosphate lithium has the de-embedding behavior of highly stable lithium ion.LiCoPO
4The theoretical specific discharge capacity of positive electrode is 167mAh/g, and the electrode potential of lithium is 4.8V relatively, is expected to become high power capacity of new generation, high-tension positive electrode.
The method of at present synthetic cobalt phosphate lithium mainly contains high temperature solid phase synthesis, Low Temperature Solid-Phase synthetic method, microwave process for synthesizing, sol-gel synthesis method, hydrothermal synthesis method etc.
High temperature solid phase synthesis is a kind of method the most commonly used in the industry preparation, and the method is by reactant by measuring than mixed grinding, and compressing tablet, then be placed in high temperature furnace at air or inert gas atmosphere sintering.As (J. Power Sources, 2005,144 (1): 226-230) adopt high temperature solid-state method, with Li such as J.Wolfenstine
2CO
3, CoC
2O
42H
2O and NH
4H
2PO
4For raw material, first under 375 ℃, process 20h, cooling after in the argon gas atmosphere stove, calcining 48h obtains end product under 775 ℃.Result of study shows the crystal morphology that obtained complete degree of crystallinity, rule and the uniform LiCoPO of particle diameter
4.Charge-discharge test shows, first discharge specific capacity is 100mAh/g under the 0.2C multiplying power.
Low-temperature solid-phase method is that a kind of solvent-free participation, reactant are two or more solid matters, and at room temperature can make the presoma of product, then by the calcining presoma, prepares the method for product.Low-temperature solid-phase method has characteristics simple to operate, also has the advantage of soft chemical method concurrently, greatly reduces simultaneously the solid phase reaction temperature, and product is significantly improved than the conventional high-temperature solid phase method on properity and exterior appearance.Natalia N.Bramnik etc. (J Solid State Electrochem, 2004,8:558-564) with (NH
4)
2HPO
4, CoCl
2With LiOH be raw material, under 600 ℃ the calcining 24 h obtain product.Adopt XRD and SEM and electrochemical property test to show, obtain complete in crystal formation, the even pure phase LiCoPO of particle diameter
4, under 0.5 C, recording first discharge specific capacity is 125mAh/g, is 75 % of theoretical capacity.
Microwave heating is to utilize heated material to absorb microwave, causes the polarization of molecule and atom, makes molecule and atom produce violent friction, causes the rising of heated material temperature.With traditional heating mode, compare, it is fast that microwave heating method has heating rate, the advantage of homogeneous heating.(the Electrochemistry Communications such as H.H.Li, 2009,11:95-98), with CH3COOLi, (CH3COO) 2Co and (NH4) 2HPO4 be raw material, first at 350 ℃ of lower preliminary treatment 2 h, then at 2.45 GHz, under the microwave of 700 W, heating 11 min obtain LiCoPO4.Test shows, synthetic sample better crystallinity degree, without dephasign.At constant current 0.5C, voltage range is under 3.0～5.1 V, and the battery first discharge specific capacity of this material is 93.3mAh/g, differs too large with theoretical capacity.
Hydro thermal method is a kind of method for preparing superfine powder that development in recent years is got up, the product powder made has crystal grain and grows complete, particle size range narrowly distributing, material phase homogeneous, better crystallinity degree, purity advantages of higher, is subject to vast battery material researcher's attention.(the Rare Metals such as Zhao Yujuan, 2009,28 (2): 117-121), adopt hydrothermal synthesis method to successfully synthesize the LiCoPO4 of rhombic system, electrochemical property test shows, adopts the synthetic material of the method under the 0.5C multiplying power, and the initial charge specific capacity is 154mAh/g, but first discharge specific capacity is only 65mAh/g, distance applications also has very large distance.
By above analysis, can find, the solid phase method sintering time is long, energy consumption is large, production efficiency is low, and the particle diameter of product distributes wayward, and uniformity, consistency, reappearance are poor.The product of microwave process for synthesizing, hydrothermal synthesis method, general particle diameter is larger, is unfavorable for the migration of lithium ion, and chemical property is undesirable.
In sum,, all there is the specific capacity high-technology problem not of the cobalt phosphate lithium positive electrode of final gained in the synthetic method of above-mentioned various cobalt phosphate lithium positive electrodes.
Summary of the invention
The objective of the invention is for the specific capacity that solves above-mentioned cobalt phosphate lithium positive electrode high-technology problem etc. and a kind of synthetic method of lithium ion battery positive pole material phosphoric acid cobalt lithium is provided not, the specific capacity of the lithium ion battery positive pole material phosphoric acid cobalt lithium of the final gained of the method is higher.
Technical scheme of the present invention
A kind of synthetic method of lithium ion anode material cobalt phosphate lithium, namely take lithium hydroxide, cobalt acetate, phosphoric acid, nitric acid, sucrose etc. and be that raw material, described raw material calculate according to the mass fraction, its form and content as follows:
Lithium hydroxide 38-46 part
Cobalt acetate 224-274 part
Phosphatase 11 05-126 part
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Its synthetic method specifically comprises the steps:
(1), the cobalt acetate of 224-274 part is dissolved in the deionized water of 300 parts and is made into the cobalt acetate aqueous solution;
The sucrose dissolved of the lithium hydroxide of 38-46 part and 15 parts is made into to lithium hydroxide/sucrose mixed solution in the deionized water of 250 parts;
Add 100 parts of deionized waters to be made into phosphoric acid solution the phosphoric acid of 105-126 part;
(2), the phosphoric acid solution of step (1) gained is joined in the cobalt acetate aqueous solution of step (1) gained under stirring, obtain claret emulsion, after stirring, the lithium hydroxide of step (1) gained/sucrose mixed solution is joined in the claret emulsion of above-mentioned gained, stir, the nitric acid that adds 15 parts, obtain precursor aqueous solution;
(3), by the precursor aqueous solution of step (2) gained under stirring, control leaving air temp and be 105 ℃ and carry out spray drying, obtain the cobalt phosphate lithium powder presoma of porous spherical structure;
(4), the cobalt phosphate lithium powder presoma of the porous spherical structure of step (3) gained is controlled to temperature in vacuum furnace be under 600-750 ℃, to carry out vacuum calcining 16-26h, obtains lithium ion battery positive pole material phosphoric acid cobalt lithium.
The shape characteristic of the lithium ion battery anode material lithium iron phosphate particle spherical in shape of above-mentioned gained, diameter is at the 2-5 micron, this spheric granules consists of more tiny cobalt phosphate lithium nano particle, the size of these nano particles is in the 200-300 nanometer, around nano particle, there is the hole of apparent in view nano-scale, the lithium ion battery positive pole material phosphoric acid cobalt lithium that is above-mentioned gained is spherical porous structure, these nano apertures, can be used as the capillary channel of electrolyte and material exchange lithium ion, thereby improve the chemical property of cobalt phosphate lithium.
The average specific discharge capacity of the lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is 138-143mAh/g, the initial charge specific capacity is 173-190mAh/g, first discharge specific capacity is 140-151mAh/g, coulombic efficiency 75.8-84.4% first circulates, 96.7-98.3% is compared in the charging constant current, threshold voltage 4.70-4.75V in electric discharge, 4.5V is with upper mounting plate rate 92.2-93.4%.
Beneficial effect of the present invention
The synthetic method of a kind of lithium ion anode material cobalt phosphate lithium of the present invention is the spraying cracking process due to what adopt.Compared with prior art, after the spraying cracking, obtain presenting of lithium ion anode material cobalt phosphate lithium product spherical, this spheric granules is comprised of the nanometer cobalt phosphate lithium crystal grain of 100-200 nanosized, the cobalt phosphate lithium particle of this nano-scale has reduced the distance of lithium ion migration, is conducive to improve the specific capacity that obtains the cobalt phosphate lithium material.Simultaneously, owing in the Pintsch process process, having gas purging, in the cobalt phosphate lithium positive electrode of acquisition, there is the fine hole of a large amount of nanometers.The existence of this nano aperture, for the storage of electrolyte provides space, provide necessary capillary channel for carrying out fast lithium ion exchanged, is conducive to improve the multiplying power property of material.
Further, after the lithium ion battery positive pole material phosphoric acid cobalt lithium of the spherical porous structure of the synthetic method gained of lithium ion anode material cobalt phosphate lithium of the present invention is assembled into button cell, under 0.5C, carry out loop test, average specific discharge capacity is 138-143mAh/g, the initial charge specific capacity is 173-190mAh/g, first discharge specific capacity is 140-151mAh/g, coulombic efficiency 75.8-84.4% first circulates, 96.7-98.3% is compared in the charging constant current, threshold voltage 4.70-4.75V in electric discharge, 4.5V is with upper mounting plate rate 92.2-93.4%.These test results show, the lithium ion anode material cobalt phosphate lithium of above-mentioned spraying cracking synthetic method gained has good electrochemical properties, is expected to apply in the electrokinetic cell field.
The accompanying drawing explanation
The XRD collection of illustrative plates of the lithium ion battery anode material lithium iron phosphate of Fig. 1, embodiment 1 gained;
The SEM figure of the lithium ion battery anode material lithium iron phosphate of Fig. 2, embodiment 1 gained;
The chemical property collection of illustrative plates of the lithium ion battery anode material lithium iron phosphate of Fig. 3, embodiment 1 gained.
Embodiment
Also the present invention is described in detail by reference to the accompanying drawings below by embodiment, but do not limit the present invention.
The preparation of battery and the method for testing of chemical property
1., the preparation of battery anode slice
The lithium ion battery positive pole material phosphoric acid cobalt lithium, conductive carbon powder, the organic binder bond Kynoar (PVDF) that obtain are calculated according to mass ratio, be lithium ion battery positive pole material phosphoric acid cobalt lithium: conductive carbon powder: the organic binder bond Kynoar is to obtain mixed powder after the ratio of 92:3:5 is mixed, by these mixed powder 10 grams, add organic solvent 1-METHYLPYRROLIDONE (NMP) 12 grams, after fully stirring, form slurry, be coated on aluminium foil surface, after oven dry, repeatedly rolling, obtain battery anode slice;
2., battery assembling and performance test
Use 2016 type half-cell assessments to obtain the chemical property of cobalt phosphate lithium.The battery anode slice punching press that rolling is good becomes the disk of 12 millimeters of diameters, accurately after its quality of weighing, according to formula, form and calculate the cobalt phosphate lithium quality in pole piece, use the import celgard barrier film of 19 millimeters of diameters, use the metal lithium sheet of 15 millimeters of diameters as negative pole, but in glove box, be assembled into test battery.
The specific capacity test of battery:
Use Wuhan Lan Dian company cell tester (Land2000) to carry out.Under the 0.5C condition, carry out repeatedly loop test.
In various embodiments of the present invention, spray drying device used is the MOBILE MINOR disk–type spray dryer that Shanghai generation biological plant far away engineering company produces.
Embodiment 1
A kind of synthetic method of lithium ion battery positive pole material phosphoric acid cobalt lithium, take lithium hydroxide, cobalt acetate, phosphoric acid, nitric acid, sucrose and deionized water and be raw material, and described raw material is calculated according to the mass fraction, its form and content as follows:
42 parts of lithium hydroxides
249 parts of cobalt acetates
15 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Its synthetic method specifically comprises the steps:
(1), the cobalt acetate of 249 parts is dissolved in the deionized water of 300 parts and is made into the cobalt acetate aqueous solution;
The sucrose dissolved of the lithium hydroxides of 42 parts and 15 parts is made into to lithium hydroxide/sucrose mixed solution in the deionized water of 250 parts;
Add the deionized water of 100 parts to be made into phosphoric acid solution the phosphoric acid of 115 parts;
(2), by the phosphoric acid solution of step (1) gained, under stirring, join the cobalt acetate aqueous solution of step (1) gained, obtain claret emulsion, after stirring, the lithium hydroxide of step (1) gained/sucrose mixed solution is joined in this claret emulsion of gained, stir, then add the nitric acid of 15 parts and stir, obtain precursor aqueous solution;
(3), by the precursor aqueous solution of step (2) gained under stirring, control leaving air temp and be 105 ℃ and carry out spray drying, obtain the cobalt phosphate lithium powder presoma of porous spherical;
(4), the cobalt phosphate lithium powder presoma of the porous spherical of step (3) gained is placed in to quartz ampoule, and then quartz ampoule is placed in to vacuum furnace, controlling temperature is to carry out vacuum calcining 21h under 680 ℃, obtains lithium ion battery positive pole material phosphoric acid cobalt lithium.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained detects by X-ray diffractometer (XRD, Rigaku Rigaku), XRD test result such as Fig. 1 of gained.In Fig. 1, can find out that diffraction maximums all in this collection of illustrative plates can demarcate the diffraction maximum into cobalt phosphate lithium, namely do not have the peak position of other materials to occur, show that the final material of the synthetic method gained of above-mentioned lithium ion battery positive pole material phosphoric acid cobalt lithium is the pure phase cobalt phosphate lithium.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained, used ESEM (SEM, NEC 6700F) to carry out the pattern detection, SEM observed result such as Fig. 2 of gained.As can be seen from Figure 2, the lithium ion battery anode material lithium iron phosphate of gained presents the shape characteristic of spheric granules, and diameter is at the 2-5 micron.This spheric granules consists of more tiny cobalt phosphate lithium nano particle, and the size of these nano particles is in the 200-300 nanometer.Around nano particle, there is the hole of apparent in view nano-scale, the lithium ion battery positive pole material phosphoric acid cobalt lithium that is above-mentioned gained is spherical porous structure, these nano apertures, can be used as the capillary channel of electrolyte and material exchange lithium ion, thereby improve the chemical property of cobalt phosphate lithium.
Using the half-cell method to be assembled into button-shaped 2016 batteries charge-discharge performance to this battery under the multiplying power of 0.5C the lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained tests, discharge and recharge result such as Fig. 3 first 5 times, as can be seen from Figure 3, average specific discharge capacity is 140mAh/g, the initial charge specific capacity is 190mAh/g, first discharge specific capacity is 144mAh/g, coulombic efficiency 75.8% first circulates, the charging constant current is than 97.4%, threshold voltage 4.72V in electric discharge, 4.5V is with upper mounting plate rate 92.2%.Show thus, the lithium ion battery anode material lithium iron phosphate of above-mentioned synthetic method gained has good electrochemical properties, can apply in the electrokinetic cell field.
Embodiment 2
A kind of synthetic method of lithium ion battery positive pole material phosphoric acid cobalt lithium, namely take lithium hydroxide, cobalt acetate, phosphoric acid, nitric acid, sucrose and deionized water and be raw material, and described raw material is calculated according to the mass fraction, its form and content as follows:
38 parts of lithium hydroxides
224 parts of cobalt acetates
05 part of phosphatase 11
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Its synthetic method specifically comprises the steps:
(1), the cobalt acetate of 224 parts is dissolved in the deionized water of 300 parts and is made into the cobalt acetate aqueous solution;
The sucrose dissolved of the lithium hydroxides of 38 parts and 15 parts is made into to lithium hydroxide/sucrose mixed solution in the deionized water of 250 parts;
Add the deionized water of 100 parts to be made into phosphoric acid solution the phosphoric acid of 105 parts;
(2), by the phosphoric acid solution of step (1) gained, under stirring, join the cobalt acetate aqueous solution of step (1) gained, obtain claret emulsion, after stirring, the lithium hydroxide of step (1) gained/sucrose mixed solution is joined in the claret emulsion of gained, stir, then add the nitric acid of 15 parts and stir, obtain precursor aqueous solution;
(3), by the precursor aqueous solution of step (2) gained under stirring, control leaving air temp and be 105 ℃ and carry out spray drying, obtain the cobalt phosphate lithium powder presoma of porous spherical;
(4), the cobalt phosphate lithium powder presoma of the porous spherical of step (3) gained is placed in to quartz ampoule, and then quartz ampoule is placed in to vacuum furnace, controlling temperature is to carry out vacuum calcining 26h under 600 ℃, obtains lithium ion battery positive pole material phosphoric acid cobalt lithium.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used X-ray diffractometer (XRD, Rigaku Rigaku) test, result is similar to Fig. 1, do not find the diffraction maximum of other phases, the final material that shows the synthetic method gained of above-mentioned lithium ion battery positive pole material phosphoric acid cobalt lithium is pure phase cobalt phosphate lithium material.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used ESEM (SEM, NEC 6700F) to carry out the SEM observation, and result is similar to Fig. 2, has equally the internal structure of spheric granules external appearance characteristic and nanoporous.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is made battery pole piece according to the method for embodiment 1, charge-discharge performance to this battery under the multiplying power of 0.5C is tested, result shows, the average specific discharge capacity of the lithium ion battery positive pole material phosphoric acid cobalt lithium of gained is 143mAh/g, the initial charge specific capacity is 182mAh/g, first discharge specific capacity is 148mAh/g, coulombic efficiency 81.3% first circulates, the charging constant current is than 97.8%, threshold voltage 4.75V in electric discharge, 4.5V is with upper mounting plate rate 93.1%.This lithium ion battery positive pole material phosphoric acid cobalt lithium that shows above-mentioned gained has good electrochemical properties.
Embodiment 3
A kind of synthetic method of lithium ion battery positive pole material phosphoric acid cobalt lithium, namely take lithium hydroxide, cobalt acetate, phosphoric acid, nitric acid, sucrose and deionized water and be raw material, and described raw material is calculated according to the mass fraction, its form and content as follows:
46 parts of lithium hydroxides
274 parts of cobalt acetates
26 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Its synthetic method specifically comprises the steps:
(1), the cobalt acetate of 274 parts is dissolved in the deionized water of 300 parts and is made into the cobalt acetate aqueous solution;
The sucrose dissolved of the lithium hydroxides of 46 parts and 15 parts is mixed with to lithium hydroxide/sucrose mixed solution in the deionized water of 250 parts;
Add the deionized water of 100 parts to be made into phosphoric acid solution the phosphoric acid of 126 parts;
(2), by the phosphoric acid solution of step (1) gained, under stirring, join the cobalt acetate aqueous solution of step (1) gained, obtain claret emulsion, after stirring, the lithium hydroxide of step (1) gained/sucrose mixed solution is joined in the claret emulsion of gained, stir, then add the nitric acid of 15 parts and stir, obtain precursor aqueous solution;
(3), by the precursor aqueous solution of step (2) gained under stirring, control leaving air temp and be 105 ℃ and carry out spray drying, obtain the cobalt phosphate lithium powder presoma of porous spherical;
(4), the cobalt phosphate lithium powder presoma of the porous spherical of step (3) gained is placed in to quartz ampoule, and then quartz ampoule is placed in to vacuum furnace, controlling temperature is to carry out vacuum calcining 16h under 750 ℃, obtains lithium ion battery positive pole material phosphoric acid cobalt lithium.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used X-ray diffractometer (XRD, Rigaku Rigaku) test, result is similar to Fig. 1, do not find the diffraction maximum of other phases, the final material that shows the synthetic method gained of above-mentioned lithium ion battery positive pole material phosphoric acid cobalt lithium is pure phase cobalt phosphate lithium material.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used ESEM (SEM, NEC 6700F) to carry out the SEM observation, and result is similar to Fig. 2, has equally the internal structure of spheric granules external appearance characteristic and nanoporous.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is made battery pole piece according to the method for embodiment 1, charge-discharge performance to this battery under the multiplying power of 0.5C is tested, result shows, the average specific discharge capacity of the lithium ion battery positive pole material phosphoric acid cobalt lithium of gained is 138mAh/g, the initial charge specific capacity is 178mAh/g, first discharge specific capacity is 141mAh/g, coulombic efficiency 79.2% first circulates, the charging constant current is than 97.6%, threshold voltage 4.74V in electric discharge, 4.5V is with upper mounting plate rate 92.9%.This lithium ion battery positive pole material phosphoric acid cobalt lithium that shows above-mentioned gained has good electrochemical properties.
Embodiment 4
A kind of synthetic method of lithium ion battery positive pole material phosphoric acid cobalt lithium, namely take lithium hydroxide, cobalt acetate, phosphoric acid, nitric acid, sucrose and deionized water and be raw material, and described raw material is calculated according to the mass fraction, its form and content as follows:
46 parts of lithium hydroxides
224 parts of cobalt acetates
15 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Its synthetic method specifically comprises the steps:
(1), the cobalt acetate of 224 parts is dissolved in the deionized water of 300 parts and is made into the cobalt acetate aqueous solution;
The sucrose dissolved of the lithium hydroxides of 46 parts and 15 parts is made into to lithium hydroxide/sucrose mixed solution in the deionized water of 250 parts;
Add the deionized water of 100 parts to be made into phosphoric acid solution the phosphoric acid of 115 parts;
(2), by the phosphoric acid solution of step (1) gained, under stirring, join the cobalt acetate aqueous solution of step (1) gained, obtain claret emulsion, after stirring, the lithium hydroxide of step (1) gained/sucrose mixed solution is joined in the claret emulsion of gained, stir, then add the nitric acid of 15 parts and stir, obtain precursor aqueous solution;
(3), by the precursor aqueous solution of step (2) gained under stirring, control leaving air temp and be 105 ℃ and carry out spray drying, obtain the cobalt phosphate lithium powder presoma of porous spherical;
(4), the cobalt phosphate lithium powder presoma of the porous spherical of step (3) gained is placed in to quartz ampoule, and then quartz ampoule is placed in to vacuum furnace, controlling temperature is to carry out vacuum calcining 26h under 680 ℃, obtains lithium ion battery positive pole material phosphoric acid cobalt lithium.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used X-ray diffractometer (XRD, Rigaku Rigaku) test, result is similar to Fig. 1, do not find the diffraction maximum of other phases, the final material that shows the synthetic method gained of above-mentioned lithium ion battery positive pole material phosphoric acid cobalt lithium is pure phase cobalt phosphate lithium material.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used ESEM (SEM, NEC 6700F) to carry out the SEM observation, and result is similar to Fig. 2, has equally the internal structure of spheric granules external appearance characteristic and nanoporous.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is made battery pole piece according to the method for embodiment 1, charge-discharge performance to this battery under the multiplying power of 0.5C is tested, result shows, the average specific discharge capacity of the lithium ion battery positive pole material phosphoric acid cobalt lithium of gained is 142mAh/g, the initial charge specific capacity is 181mAh/g, first discharge specific capacity is 147mAh/g, coulombic efficiency 81.2% first circulates, the charging constant current is than 98.2%, threshold voltage 4.70V in electric discharge, 4.5V is with upper mounting plate rate 93.4%.This lithium ion battery positive pole material phosphoric acid cobalt lithium that shows above-mentioned gained has good electrochemical properties.
Embodiment 5
A kind of synthetic method of lithium ion battery positive pole material phosphoric acid cobalt lithium, namely take lithium hydroxide, cobalt acetate, phosphoric acid, nitric acid, sucrose and deionized water and be raw material, and described raw material is calculated according to the mass fraction, its form and content as follows:
38 parts of lithium hydroxides
249 parts of cobalt acetates
26 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Its synthetic method specifically comprises the steps:
(1), the cobalt acetate of 249 parts is dissolved in the deionized water of 300 parts and is made into the cobalt acetate aqueous solution;
The sucrose dissolved of the lithium hydroxides of 38 parts and 15 parts is made into to lithium hydroxide/sucrose mixed solution in the deionized water of 250 parts;
Add the deionized water of 100 parts to be made into phosphoric acid solution the phosphoric acid of 126 parts;
(2), by the phosphoric acid solution of step (1) gained, under stirring, join the cobalt acetate aqueous solution of step (1) gained, obtain claret emulsion, after stirring, the lithium hydroxide of step (1) gained/sucrose mixed solution is joined in the claret emulsion of gained, stir, then add the nitric acid of 15 parts and stir, obtain precursor aqueous solution;
(3), by the precursor aqueous solution of step (2) gained under stirring, control leaving air temp and be 105 ℃ and carry out spray drying, obtain the cobalt phosphate lithium powder presoma of porous spherical;
(4), the cobalt phosphate lithium powder presoma of the porous spherical of step (3) gained is placed in to quartz ampoule, and then quartz ampoule is placed in to vacuum furnace, controlling temperature is to carry out vacuum calcining 21h under 750 ℃, obtains lithium ion battery positive pole material phosphoric acid cobalt lithium.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used X-ray diffractometer (XRD, Rigaku Rigaku) test, result is similar to Fig. 1, do not find the diffraction maximum of other phases, the final material that shows the synthetic method gained of above-mentioned lithium ion battery positive pole material phosphoric acid cobalt lithium is pure phase cobalt phosphate lithium material.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used ESEM (SEM, NEC 6700F) to carry out the SEM observation, and result is similar to Fig. 2, has equally the internal structure of spheric granules external appearance characteristic and nanoporous.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is made battery pole piece according to the method for embodiment 1, charge-discharge performance to this battery under the multiplying power of 0.5C is tested, result shows, the average specific discharge capacity of the lithium ion battery positive pole material phosphoric acid cobalt lithium of gained is 136mAh/g, the initial charge specific capacity is 184mAh/g, first discharge specific capacity is 140mAh/g, coulombic efficiency 76.1% first circulates, the charging constant current is than 96.7%, threshold voltage 4.67V in electric discharge, 4.5V is with upper mounting plate rate 92.4%.This lithium ion battery positive pole material phosphoric acid cobalt lithium that shows above-mentioned gained has good electrochemical properties.
Embodiment 6
A kind of synthetic method of lithium ion battery positive pole material phosphoric acid cobalt lithium, namely take lithium hydroxide, cobalt acetate, phosphoric acid, nitric acid, sucrose and deionized water and be raw material, and described raw material is calculated according to the mass fraction, its form and content as follows:
42 parts of lithium hydroxides
274 parts of cobalt acetates
05 part of phosphatase 11
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Its synthetic method specifically comprises the steps:
Specifically comprise the steps:
(1), the cobalt acetate of 274 parts is dissolved in the deionized water of 300 parts and is made into the cobalt acetate aqueous solution;
The sucrose dissolved of the lithium hydroxides of 42 parts and 15 parts is made into to lithium hydroxide/sucrose mixed solution in the deionized water of 250 parts;
Add the deionized water of 100 parts to be made into phosphoric acid solution the phosphoric acid of 105 parts;
(2), by the phosphoric acid solution of step (1) gained, under stirring, join the cobalt acetate solution of step (1) gained, obtain claret emulsion, after stirring, the lithium hydroxide of step (1) gained/sucrose mixed solution is joined in the claret emulsion of gained, stir, then add the nitric acid of 15 parts and stir, obtain precursor aqueous solution;
(3), by the precursor aqueous solution of step (2) gained under stirring, control leaving air temp and be 105 ℃ and carry out spray drying, obtain the cobalt phosphate lithium powder presoma of porous spherical;
(4), the cobalt phosphate lithium powder presoma of the porous spherical of step (3) gained is placed in to quartz ampoule, and then quartz ampoule is placed in to vacuum furnace, controlling temperature is to carry out vacuum calcining 21h under 600 ℃, obtains lithium ion battery positive pole material phosphoric acid cobalt lithium.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used X-ray diffractometer (XRD, Rigaku Rigaku) test, result is similar to Fig. 1, do not find the diffraction maximum of other phases, the final material that shows the synthetic method gained of above-mentioned lithium ion battery positive pole material phosphoric acid cobalt lithium is pure phase cobalt phosphate lithium material.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used ESEM (SEM, NEC 6700F) to carry out the SEM observation, and result is similar to Fig. 2, has equally the internal structure of spheric granules external appearance characteristic and nanoporous.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is made battery pole piece according to the method for embodiment 1, charge-discharge performance to this battery under the multiplying power of 0.5C is tested, result shows, the average specific discharge capacity of the lithium ion battery positive pole material phosphoric acid cobalt lithium of gained is 142mAh/g, the initial charge specific capacity is 176mAh/g, first discharge specific capacity is 148mAh/g, coulombic efficiency 84.1% first circulates, the charging constant current is than 97.1%, threshold voltage 4.73V in electric discharge, 4.5V is with upper mounting plate rate 92.8%.This lithium ion battery positive pole material phosphoric acid cobalt lithium that shows above-mentioned gained has good electrochemical properties.
Embodiment 7
A kind of synthetic method of lithium ion battery positive pole material phosphoric acid cobalt lithium, namely take lithium hydroxide, cobalt acetate, phosphoric acid, nitric acid, sucrose and deionized water and be raw material, and described raw material is calculated according to the mass fraction, its form and content as follows:
38 parts of lithium hydroxides
249 parts of cobalt acetates
05 part of phosphatase 11
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Its synthetic method specifically comprises the steps:
(1), the cobalt acetate of 249 parts is dissolved in the deionized water of 300 parts and is made into the cobalt acetate aqueous solution;
The sucrose dissolved of the lithium hydroxides of 38 parts and 15 parts is made into to lithium hydroxide/sucrose mixed solution in the deionized water of 250 parts;
Add the deionized water of 100 parts to be made into phosphoric acid solution the phosphoric acid of 105 parts;
(2), by the phosphoric acid solution of step (1) gained, under stirring, join the cobalt acetate aqueous solution of step (1) gained, obtain claret emulsion, after stirring, the lithium hydroxide of step (1) gained/sucrose mixed solution is joined in the claret emulsion of gained, stir, then add the nitric acid of 15 parts and stir, obtain precursor aqueous solution;
(3), by the precursor aqueous solution of step (2) gained under stirring, control leaving air temp and be 105 ℃ and carry out spray drying, obtain the cobalt phosphate lithium powder presoma of porous spherical;
(4), the cobalt phosphate lithium powder presoma of the porous spherical of step (3) gained is placed in to quartz ampoule, and then quartz ampoule is placed in to vacuum furnace, controlling temperature is to carry out vacuum calcining 16h under 750 ℃, obtains lithium ion battery positive pole material phosphoric acid cobalt lithium.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used X-ray diffractometer (XRD, Rigaku Rigaku) test, result is similar to Fig. 1, do not find the diffraction maximum of other phases, the final material that shows the synthetic method gained of above-mentioned lithium ion battery positive pole material phosphoric acid cobalt lithium is pure phase cobalt phosphate lithium material.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used ESEM (SEM, NEC 6700F) to carry out the SEM observation, and result is similar to Fig. 2, has equally the internal structure of spheric granules external appearance characteristic and nanoporous.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is made battery pole piece according to the method for embodiment 1, charge-discharge performance to this battery under the multiplying power of 0.5C is tested, result shows, the average specific discharge capacity of the lithium ion battery positive pole material phosphoric acid cobalt lithium of gained is 140mAh/g, the initial charge specific capacity is 173mAh/g, first discharge specific capacity is 146mAh/g, coulombic efficiency 84.4% first circulates, the charging constant current is than 98.3%, threshold voltage 4.68V in electric discharge, 4.5V is with upper mounting plate rate 93.2%.This lithium ion battery positive pole material phosphoric acid cobalt lithium that shows above-mentioned gained has good electrochemical properties.
Embodiment 8
A kind of synthetic method of lithium ion battery positive pole material phosphoric acid cobalt lithium, namely take lithium hydroxide, cobalt acetate, phosphoric acid, nitric acid, sucrose and deionized water and be raw material, and described raw material is calculated according to the mass fraction, its form and content as follows:
38 parts of lithium hydroxides
249 parts of cobalt acetates
26 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Its synthetic method specifically comprises the steps:
Specifically comprise the steps:
(1), the cobalt acetate of 249 parts is dissolved in the deionized water of 300 parts and is made into the cobalt acetate aqueous solution;
The sucrose dissolved of the lithium hydroxides of 38 parts and 15 parts is made into to lithium hydroxide/sucrose mixed solution in the deionized water of 250 parts;
Add the deionized water of 100 parts to be made into phosphoric acid solution the phosphoric acid of 126 parts;
(2), by the phosphoric acid solution of step (1) gained, under stirring, join the cobalt acetate aqueous solution of step (1) gained, obtain claret emulsion, after stirring, the lithium hydroxide of step (1) gained/sucrose mixed solution is joined in the claret emulsion of gained, stir, then add the nitric acid of 15 parts and stir, obtain precursor aqueous solution;
(3), by the precursor aqueous solution of step (2) gained under stirring, control leaving air temp and be 105 ℃ and carry out spray drying, obtain the cobalt phosphate lithium powder presoma of porous spherical;
(4), the cobalt phosphate lithium powder presoma of the porous spherical of step (1) gained is placed in to quartz ampoule, and then quartz ampoule is placed in to vacuum furnace, controlling temperature is under 600 ℃, to carry out high-temperature vacuum calcining 16h, obtains lithium ion battery positive pole material phosphoric acid cobalt lithium.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used X-ray diffractometer (XRD, Rigaku Rigaku) test, result is similar to Fig. 1, do not find the diffraction maximum of other phases, the final material that shows the synthetic method gained of above-mentioned lithium ion battery positive pole material phosphoric acid cobalt lithium is pure phase cobalt phosphate lithium material.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used ESEM (SEM, NEC 6700F) to carry out the SEM observation, and result is similar to Fig. 2, has equally the internal structure of spheric granules external appearance characteristic and nanoporous.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is made battery pole piece according to the method for embodiment 1, charge-discharge performance to this battery under the multiplying power of 0.5C is tested, result shows, the average specific discharge capacity of the lithium ion battery positive pole material phosphoric acid cobalt lithium of gained is 143mAh/g, the initial charge specific capacity is 178mAh/g, first discharge specific capacity is 151mAh/g, coulombic efficiency 80.3% first circulates, the charging constant current is than 97.8%, threshold voltage 4.72V in electric discharge, 4.5V is with upper mounting plate rate 92.6%.This lithium ion battery positive pole material phosphoric acid cobalt lithium that shows above-mentioned gained has good electrochemical properties.
Embodiment 9
A kind of synthetic method of lithium ion battery positive pole material phosphoric acid cobalt lithium, namely take lithium hydroxide, cobalt acetate, phosphoric acid, nitric acid, sucrose and deionized water and be raw material, and described raw material is calculated according to the mass fraction, its form and content as follows:
42 parts of lithium hydroxides
249 parts of cobalt acetates
15 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Its synthetic method specifically comprises the steps:
(1), the cobalt acetate of 249 parts is dissolved in the deionized water of 300 parts and is made into the cobalt acetate aqueous solution;
The sucrose dissolved of the lithium hydroxides of 42 parts and 15 parts is made into to lithium hydroxide/sucrose mixed solution in the deionized water of 250 parts;
Add the deionized water of 100 parts to be made into phosphoric acid solution the phosphoric acid of 115 parts;
(2), by the phosphoric acid solution of step (1) gained, under stirring, join the cobalt acetate aqueous solution of step (1) gained, obtain claret emulsion, after stirring, the lithium hydroxide of step (1) gained/sucrose mixed solution is joined in the claret emulsion of gained, stir, then add the nitric acid of 15 parts and stir, obtain precursor aqueous solution;
(3), by the precursor aqueous solution of step (2) gained under stirring, control leaving air temp and be 105 ℃ and carry out spray drying, obtain the cobalt phosphate lithium powder presoma of porous spherical;
(4), the cobalt phosphate lithium powder presoma of the porous spherical of step (3) gained is placed in to quartz ampoule, and then quartz ampoule is placed in to vacuum furnace, controlling temperature is to carry out vacuum calcining 26h under 750 ℃, obtains lithium ion battery positive pole material phosphoric acid cobalt lithium.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used X-ray diffractometer (XRD, Rigaku Rigaku) test, result is similar to Fig. 1, do not find the diffraction maximum of other phases, the final material that shows the synthetic method gained of above-mentioned lithium ion battery positive pole material phosphoric acid cobalt lithium is pure phase cobalt phosphate lithium material.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is used ESEM (SEM, NEC 6700F) to carry out the SEM observation, and result is similar to Fig. 2, has equally the internal structure of spheric granules external appearance characteristic and nanoporous.
The lithium ion battery positive pole material phosphoric acid cobalt lithium of above-mentioned gained is made battery pole piece according to the method for embodiment 1, charge-discharge performance to this battery under the multiplying power of 0.5C is tested, result shows, the average specific discharge capacity of the lithium ion battery positive pole material phosphoric acid cobalt lithium of gained is 138mAh/g, the initial charge specific capacity is 183mAh/g, first discharge specific capacity is 151mAh/g, coulombic efficiency 82.5% first circulates, the charging constant current is than 97.1%, threshold voltage 4.75V in electric discharge, 4.5V is with upper mounting plate rate 92.6%.This lithium ion battery positive pole material phosphoric acid cobalt lithium that shows above-mentioned gained has good electrochemical properties.
In sum, the synthetic method of a kind of lithium ion battery positive pole material phosphoric acid cobalt lithium of the present invention, namely using cobalt acetate, lithium hydroxide, phosphoric acid etc. as raw material, and the lithium ion battery positive pole material phosphoric acid cobalt lithium obtained by steps such as spray drying and vacuum calcinings is the pure phase cobalt phosphate.And this synthetic method operating process is simple.The lithium ion battery positive pole material phosphoric acid cobalt lithium of gained presents the porous spherical structure, and pore size is even, and pattern is unified, for lithium ion exchanged provides capillary channel.The electrochemical property test structure shows, this lithium ion battery positive pole material phosphoric acid cobalt lithium has chemical property preferably, can be applied in the electrokinetic cell field.
Foregoing is the basic explanation under conceiving for the present invention only, and, according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (10)
1. the synthetic method of a lithium ion battery positive pole material phosphoric acid cobalt lithium, is characterized in that take that lithium hydroxide, cobalt acetate, phosphoric acid, nitric acid, sucrose and deionized water are raw material, and described raw material is calculated according to the mass fraction, and its composition and content are as follows:
Lithium hydroxide 38-46 part
Cobalt acetate 224-274 part
Phosphatase 11 05-126 part
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Its synthetic method specifically comprises the steps:
(1), the cobalt acetate of 224-274 part is dissolved in the deionized water of 300 parts and is made into the cobalt acetate aqueous solution;
The sucrose dissolved of the lithium hydroxide of 38-46 part and 15 parts is made into to lithium hydroxide/sucrose mixed solution in the deionized water of 250 parts;
Add 100 parts of deionized waters to be made into phosphoric acid solution the phosphoric acid of 105-126 part;
(2), the phosphoric acid solution of step (1) gained is joined in the cobalt acetate aqueous solution of step (1) gained under stirring, obtain claret emulsion, after stirring, the lithium hydroxide of step (1) gained/sucrose mixed solution is joined in the claret emulsion of above-mentioned gained, stir, the nitric acid that adds 15 parts, obtain precursor aqueous solution;
(3), by the precursor aqueous solution of step (2) gained under stirring, control leaving air temp and be 105 ℃ and carry out spray drying, obtain the cobalt phosphate lithium powder presoma of porous spherical structure;
(4), the cobalt phosphate lithium powder presoma of the porous spherical structure of step (3) gained is controlled to temperature in vacuum furnace be under 600-750 ℃, to carry out vacuum calcining 16-26h, obtains lithium ion battery positive pole material phosphoric acid cobalt lithium.
2. the synthetic method of a kind of lithium ion battery positive pole material phosphoric acid cobalt lithium as claimed in claim 1, is characterized in that described raw material, calculates according to the mass fraction, and its composition and content are as follows:
42 parts of lithium hydroxides
249 parts of cobalt acetates
15 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters
Vacuum calcining described in step (4), namely controlling temperature is 680 ℃, the time is 21h.
3. the synthetic method of a kind of lithium ion battery positive pole material phosphoric acid cobalt lithium as claimed in claim 1, is characterized in that described raw material, calculates according to the mass fraction, and its composition and content are as follows:
38 parts of lithium hydroxides
224 parts of cobalt acetates
05 part of phosphatase 11
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Vacuum calcining described in step (4), namely controlling temperature is 600 ℃, the time is 26h.
4. the synthetic method of a kind of lithium ion battery positive pole material phosphoric acid cobalt lithium as claimed in claim 1, is characterized in that described raw material, calculates according to the mass fraction, and its composition and content are as follows:
46 parts of lithium hydroxides
274 parts of cobalt acetates
26 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Vacuum calcining described in step (4), namely controlling temperature is 750 ℃, the time is 16h.
5. the synthetic method of a kind of lithium ion battery positive pole material phosphoric acid cobalt lithium as claimed in claim 1, is characterized in that described raw material, calculates according to the mass fraction, and its composition and content are as follows:
46 parts of lithium hydroxides
224 parts of cobalt acetates
15 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters
Vacuum calcining described in step (4), namely controlling temperature is 680 ℃, the time is 26h.
6. the synthetic method of a kind of lithium ion battery positive pole material phosphoric acid cobalt lithium as claimed in claim 1, is characterized in that described raw material, calculates according to the mass fraction, and its composition and content are as follows:
38 parts of lithium hydroxides
249 parts of cobalt acetates
26 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Vacuum calcining described in step (4), namely controlling temperature is 750 ℃, the time is 21h.
7. the synthetic method of a kind of lithium ion battery positive pole material phosphoric acid cobalt lithium as claimed in claim 1, is characterized in that described raw material, calculates according to the mass fraction, and its composition and content are as follows:
42 parts of lithium hydroxides
274 parts of cobalt acetates
05 part of phosphatase 11
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Vacuum calcining described in step (4), namely controlling temperature is 600 ℃, the time is 21h.
8. the synthetic method of a kind of lithium ion battery positive pole material phosphoric acid cobalt lithium as claimed in claim 1, is characterized in that described raw material, calculates according to the mass fraction, and its composition and content are as follows:
38 parts of lithium hydroxides
249 parts of cobalt acetates
05 part of phosphatase 11
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Vacuum calcining described in step (4), namely controlling temperature is 750 ℃, the time is 16h.
9. the synthetic method of a kind of lithium ion battery positive pole material phosphoric acid cobalt lithium as claimed in claim 1, is characterized in that described raw material, calculates according to the mass fraction, and its composition and content are as follows:
38 parts of lithium hydroxides
249 parts of cobalt acetates
26 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Vacuum calcining described in step (4), namely controlling temperature is 600 ℃, the time is 16h.
10. the synthetic method of a kind of lithium ion battery positive pole material phosphoric acid cobalt lithium as claimed in claim 1, is characterized in that described raw material, calculates according to the mass fraction, and its composition and content are as follows:
42 parts of lithium hydroxides
249 parts of cobalt acetates
15 parts of phosphatase 11s
15 parts, nitric acid
15 parts of sucrose
650 parts of deionized waters;
Vacuum calcining described in step (4), namely controlling temperature is 750 ℃, the time is 26h.
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Cited By (6)
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| CN103754856A (en) * | 2014-01-24 | 2014-04-30 | 南京工业大学 | Preparation method of positive electrode material lithium cobalt phosphate for lithium ion battery |
| CN105576204A (en) * | 2015-12-23 | 2016-05-11 | 厦门大学 | Graphene composite carbon-coated cobalt-lithium phosphate material and preparation methods and application thereof |
| CN105810905A (en) * | 2016-03-15 | 2016-07-27 | 浙江大学 | Positive electrode material with hierarchical structure for lithium ion battery and preparation method and application of positive electrode material |
| CN109775682A (en) * | 2019-01-30 | 2019-05-21 | 鲍君杰 | A kind of preparation method of cobalt phosphate lithium |
| CN115667135A (en) * | 2020-05-25 | 2023-01-31 | Fdk株式会社 | Method for producing lithium cobalt pyrophosphate and method for producing solid battery |
| TWI804647B (en) * | 2018-07-10 | 2023-06-11 | 日商日本化學工業股份有限公司 | Method of manufacturing lithium cobalt phosphate and method of manufacturing carbon composite of lithium cobalt phosphate |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103754856A (en) * | 2014-01-24 | 2014-04-30 | 南京工业大学 | Preparation method of positive electrode material lithium cobalt phosphate for lithium ion battery |
| CN103754856B (en) * | 2014-01-24 | 2016-08-24 | 南京工业大学 | Preparation method of positive electrode material lithium cobalt phosphate for lithium ion battery |
| CN105576204A (en) * | 2015-12-23 | 2016-05-11 | 厦门大学 | Graphene composite carbon-coated cobalt-lithium phosphate material and preparation methods and application thereof |
| CN105576204B (en) * | 2015-12-23 | 2018-10-09 | 厦门大学 | A kind of compound carbon coating cobalt phosphate lithium material of graphene and the preparation method and application thereof |
| CN105810905A (en) * | 2016-03-15 | 2016-07-27 | 浙江大学 | Positive electrode material with hierarchical structure for lithium ion battery and preparation method and application of positive electrode material |
| CN105810905B (en) * | 2016-03-15 | 2018-06-22 | 浙江大学 | A kind of anode material for lithium-ion batteries with hierarchical structure, preparation method and applications |
| TWI804647B (en) * | 2018-07-10 | 2023-06-11 | 日商日本化學工業股份有限公司 | Method of manufacturing lithium cobalt phosphate and method of manufacturing carbon composite of lithium cobalt phosphate |
| CN109775682A (en) * | 2019-01-30 | 2019-05-21 | 鲍君杰 | A kind of preparation method of cobalt phosphate lithium |
| CN109775682B (en) * | 2019-01-30 | 2021-01-29 | 鲍君杰 | Preparation method of lithium cobalt phosphate |
| CN115667135A (en) * | 2020-05-25 | 2023-01-31 | Fdk株式会社 | Method for producing lithium cobalt pyrophosphate and method for producing solid battery |
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