CN109449431A - A method of preparing lithium battery size tunable cobalt phosphate lithium composite positive pole - Google Patents

A method of preparing lithium battery size tunable cobalt phosphate lithium composite positive pole Download PDF

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CN109449431A
CN109449431A CN201811538394.0A CN201811538394A CN109449431A CN 109449431 A CN109449431 A CN 109449431A CN 201811538394 A CN201811538394 A CN 201811538394A CN 109449431 A CN109449431 A CN 109449431A
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weight
sio
positive pole
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CN109449431B (en
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蒋涛
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Jiangxi Huahao new energy Co.,Ltd.
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Chengdu Qiqi Decimal Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to the technical fields of anode material of lithium battery, provide a kind of method for preparing lithium battery size tunable cobalt phosphate lithium composite positive pole.This method is first prepared for particle size and is distributed controllable SiO2Particle, then with SiO2Particle is that hollow nitrogen-doped carbon particle is made in template, polythiophene doping phosphoric acid cobalt lithium is further formed in the hollow hole of carbon particle, obtained N doping carbon-coating is shell, the composite positive pole that polythiophene doping phosphoric acid cobalt lithium is core.It is compared with the traditional method, preparation method of the invention, had not only realized effective control to cobalt phosphate lithium particle size and distribution, but also improve the electric conductivity and cyclical stability of material.

Description

A method of preparing lithium battery size tunable cobalt phosphate lithium composite positive pole
Technical field
The invention belongs to the technical field of anode material of lithium battery, provides and a kind of prepare lithium battery size tunable phosphoric acid The method of cobalt lithium composite positive pole.
Background technique
Lithium battery is the battery that performance is extremely excellent in secondary chemical sources of electric energy, and the performances such as energy density, cycle life are dominant Lithium ion battery is set to become development trend.The performance of lithium battery depends primarily on the structure and performance of inside battery material used. The raw material of lithium ion battery mainly include positive and negative pole material, electrolyte, electrode base material, isolation film and tank material etc..Wherein, positive Material is raw material the most key in lithium battery, since positive electrode occupies larger proportion (positive and negative electrode in lithium ion battery The mass ratio of material is 3:1 ~ 4:1), therefore the research of high performance positive electrode is always lithium ion battery industry development Emphasis.
In currently in use and exploitation anode material of lithium battery, the performance shown with transition metal oxide is most It is good.Wherein, cobalt phosphate lithium has many advantages, such as that operating voltage and energy density are high, safety is good.Its synthetic method has very much, mainly There are solid reaction process, sol-gel method, hydrothermal/solvent thermal method, microwave method, spray heating decomposition etc..Due to point of particle size Cloth has the performance of positive electrode important influence, thus improves the synthetic method of material, controls the particle size of material And size distribution, the good material of dispersion performance is prepared, Li is improved+Diffusion rate, be that optimization cobalt phosphate lithium positive electrode is comprehensive The key of performance.
Chinese invention patent application number 201611005490.X discloses a kind of preparation method of cobalt phosphate lithium positive electrode. The material while carbon coated and graphene, wherein carbon and graphene have certain content, and preparation method is through ball milling mixing and surpasses Sonication, and reasonable restriction has been made to calcination temperature and time.The method of the invention can improve leading for cobalt phosphate lithium positive electrode Electrically, it but can not control effectively to particle size and distribution.
Chinese invention patent application number 201510973998.8 discloses a kind of compound carbon coating cobalt phosphate lithium material of graphene Material and the preparation method and application thereof.The compound carbon coating cobalt phosphate lithium material of graphene is made of cobalt phosphate lithium and graphene and carbon, Compound by symbiosis in situ between cobalt phosphate lithium and graphene and carbon three, graphene and generated in-situ carbon constitute three-dimensional conductive Network.Method one: it is soluble in water by lithium source, cobalt source, phosphorus source and organic carbon source, obtain solution A；Disperse graphene in anhydrous second In alcohol, solution B is obtained；Solution A and B are mixed, precursor powder is obtained after spray drying, calcines under protective atmosphere, then cools down To room temperature to get.Method two: lithium source, cobalt source, phosphorus source is soluble in water, cobalt phosphate lithium presoma is obtained after spray drying；By phosphoric acid After cobalt lithium presoma is mixed with graphene and organic carbon source, calcined under protective atmosphere, then cool to room temperature to get.The hair Although bright method improves the electric conductivity and cyclical stability of cobalt phosphate lithium positive electrode, but it is poor to still remain particle diameter distribution Defect.
In conclusion the method for prior art preparation cobalt phosphate lithium, it is difficult to realize cobalt phosphate lithium particle size and distribution Effectively control, and cobalt phosphate lithium material itself is conductive and therefore the poor defect of cyclical stability develops a kind of grain Diameter size and distribution is controllable, electric conductivity and the good cobalt phosphate lithium positive electrode of cyclical stability, has great significance.
Summary of the invention
The method of prior art preparation cobalt phosphate lithium, it is difficult to realize effective control of cobalt phosphate lithium particle size and distribution, And cobalt phosphate lithium material itself is conductive and the poor defect of cyclical stability.Lithium electricity is prepared the invention proposes a kind of The method of pond size tunable cobalt phosphate lithium composite positive pole can be made particle size and be distributed controllable cobalt phosphate lithium just Pole material, and improve the electric conductivity and cyclical stability of material.
To achieve the above object, specific technical solution of the present invention is as follows:
A method of preparing lithium battery size tunable cobalt phosphate lithium composite positive pole, the cobalt phosphate lithium anode composite material The step of material preparation, is as follows:
(1) ammonium hydroxide, ethyl alcohol, deionized water are mixed by certain volume ratio, then positive silicon is added in 40 ~ 60min of magnetic agitation Acetoacetic ester is heated and is stirred to react, is cooled to room temperature after the reaction was completed, is washed repeatedly using ethyl alcohol and deionized water, and 50 ~ 60 DEG C 8 ~ 12h of lower vacuum drying is made particle size and is distributed controllable SiO2Particle；
(2) deionized water is heated to 70 ~ 90 DEG C, is gradually added into Lauxite and glucose under stirring, until the two is It is not redissolved, is filtered to remove undissolved part, obtain mixing saturated solution；
(3) by SiO2Particle is added in mixing saturated solution, 20 ~ 30min is first dispersed with stirring, then by temperature under stirring 10 ~ 20 DEG C are slowly dropped to, Lauxite and glucose moiety are precipitated and are coated on SiO2Particle surface, filtering, obtains ureaformaldehyde tree Rouge and glucose are shell, SiO2For the compound particle of core；
(4) compound particle that step (3) obtains is placed in vacuum tube furnace, is passed through nitrogen, then with the speed of 3 ~ 5 DEG C/min 650 ~ 700 DEG C are warming up to, 2 ~ 3h is kept the temperature, so that Lauxite and glucose is carbonized, is taken out after cooling, obtained N doping carbon-coating is Shell, SiO2For the compound particle of core；
(5) compound particle that step (4) obtains is placed in sodium hydroxide solution, 2 ~ 2.5h is impregnated at 70 ~ 80 DEG C and is removed SiO2Then kernel is cooled down, is filtered, washed to neutrality, 4 ~ 6h is dried in vacuo at 80 ~ 90 DEG C, hollow nitrogen-doped carbon particle is made；
(6) hollow nitrogen-doped carbon particle, nanometer polythiophene are added in deionized water and are stirred 20 ~ 40min, hydrogen-oxygen is then added Change lithium, cobalt carbonate, ammonium phosphate and stir 10 ~ 20min, is transferred in hydrothermal reaction kettle and is reacted, taken out after cooling, filter, It washs, 10 ~ 12h is dried in vacuo at 50 ~ 60 DEG C, obtained N doping carbon-coating is shell, polythiophene doping phosphoric acid cobalt lithium is the compound of core Particle, i.e. lithium battery size tunable cobalt phosphate lithium composite positive pole.
Preferably, the parts by volume of step (1) each raw material is 0.7 ~ 0.9 parts by volume of ammonium hydroxide, 75.1 ~ 81.3 body of ethyl alcohol Product part, 15 ~ 20 parts by volume of deionized water, 3 ~ 4 parts by volume of ethyl orthosilicate.
Preferably, step (1) reaction temperature is 55 ~ 60 DEG C, and the time is 2 ~ 3h.
Studies have shown that SiO prepared by the present invention2The uniform particle diameter of particle, and particle size can be by changing ammonium hydroxide Dosage is adjusted.When the parts by volume of ammonium hydroxide increases, SiO obtained2The partial size of particle increases.The ammonium hydroxide volume that the present invention is applicable in Preferably 0.7 ~ 0.9 part of part, corresponding SiO obtained2The partial size of particle is 80 ~ 200nm.
Since the solubility with temperature of Lauxite and glucose in deionized water increases and increase, obtains at high temperature Saturated solution, with the reduction of temperature, solubility reduces, and solute can gradually be precipitated, the journey that the amount and solubility of precipitation reduce Degree is related.The present invention utilizes this principle, by SiO2Particle is scattered in the high temperature saturated solution of Lauxite and glucose in advance In, as solution temperature is down to 10 ~ 20 DEG C from 70 ~ 90 DEG C, Lauxite and glucose are gradually precipitated and with SiO2Particle is core It is coated.Cooling extent is bigger, and the solute of precipitation is more, and the clad average thickness of formation is bigger, therefore, in SiO2Particle Size tunable on the basis of, the average thickness of Lauxite and glucose clad is also controllable.Preferably, step (3) is described The parts by weight of each raw material are SiO235 ~ 40 parts by weight of particle, mixing 60 ~ 65 parts by weight of saturated solution.
The cooling rate of saturated solution is faster, and the speed that solute is precipitated is also faster, the thickness uniformity of the clad of formation Poorer, in the present invention, to obtain thickness more uniform Lauxite and glucose clad, cooling rate is no more than 3 ℃/min.If cooling rate is excessively slow, prepare required overlong time be also it is worthless, therefore, as of the invention excellent Scheme is selected, step (3) cooling rate is 1 ~ 3 DEG C/min.
By high temperature sintering, so that Lauxite and glucose is carbonized, form N doping carbon-coating.Due to Lauxite and grape The average thickness and the thickness uniformity of sugared clad can be controlled by cooling extent and cooling rate, therefore corresponding N doping The thickness and its uniformity of carbon-coating are also controllable.
Step (5) is removing SiO using sodium hydroxide solution etching2When kernel, it is preferred that the sodium hydroxide solution Molar concentration is 1mol/L.
It, can be by nanometer polythiophene, hydrogen-oxygen since the hollow nitrogen-doped carbon particle obtained after etching has good adsorptivity Change lithium, cobalt carbonate, ammonium phosphate to be adsorbed in its cavity, the polythiophene doping phosphoric acid cobalt lithium for generating hydro-thermal reaction is wrapped in carbon Intragranular portion, forming N doping carbon-coating is shell, the composite particles that polythiophene doping phosphoric acid cobalt lithium is core.Hollow nitrogen-doped carbon particle is With SiO2Particle is then to have SiO using the polythiophene doping phosphoric acid cobalt lithium that carbon particle is formed as antitemplate made from template2Grain The particle size and distribution of son result in particle size and are distributed controllable cobalt phosphate lithium particle.
Polythiophene is good conductive polymer material, polythiophene to the doping of cobalt phosphate lithium be remarkably improved material from Electron conductivity and electronic conductivity.And on the one hand N doping carbon-coating further increases the conduction of material to the cladding of cobalt phosphate lithium Property, on the other hand improve the cyclical stability of positive electrode.
Preferably, the parts by weight of step (6) each raw material are hollow 3 ~ 5 parts by weight of nitrogen-doped carbon particle, the poly- thiophene of nanometer 1 ~ 2 parts by weight of pheno, 4 ~ 6 parts by weight of lithium hydroxide, 16 parts by weight of cobalt carbonate, 20 parts by weight of ammonium phosphate, 51 ~ 56 weight of deionized water Part.
Preferably, the partial size of step (6) the nanometer polythiophene is 10 ~ 20nm.
Preferably, the temperature of step (6) described hydro-thermal reaction is 170 ~ 180 DEG C, and the time is 8 ~ 10h.
The average grain diameter of positive electrode produced by the present invention, can be by the parts by volume of ammonium hydroxide to partial size between 80 ~ 200nm Size is controlled, and partial size polydispersity index is 0.01 ~ 0.03, and electronic conductivity is 1.5 ~ 1.7 × 10-1S/cm, ionic conductance Rate is 1.0 ~ 1.2 × 10-1S/cm, first charge-discharge of the manufactured positive plate after assembling manufactured button cell, under 1C multiplying power Specific capacity is 155 ~ 160mAh/g, and 50 Zhou Houwei capacity retention ratio of charge and discharge cycles is 90 ~ 92%, 100 Zhou Houwei of charge and discharge cycles Capacity retention ratio is 84 ~ 86%.
In conclusion the present invention provides a kind of sides for preparing lithium battery size tunable cobalt phosphate lithium composite positive pole Method, compared with prior art, the feature and excellent effect protruded are:
1. preparation method of the invention first prepares particle size and is distributed controllable SiO2Particle, then with SiO2Particle is Template prepares hollow nitrogen-doped carbon particle, then prepares polythiophene doping phosphoric acid cobalt lithium by antitemplate of hollow nitrogen-doped carbon particle Grain realizes effective control to cobalt phosphate lithium particle size and distribution.
2. preparation method of the invention, is doped cobalt phosphate lithium with polythiophene, the ion-conductance of material is significantly improved Conductance and electronic conductivity.
3. preparation method of the invention, coats cobalt phosphate lithium with N doping carbon-coating, the conduction of material has both been improved Property, and the cyclical stability of material is improved, especially by the control to cooling extent and cooling rate, it can control ureaformaldehyde tree The average thickness and the thickness uniformity of rouge and glucose clad, and then realize to the thickness of N doping carbon-coating and its uniformity Control.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) ammonium hydroxide, ethyl alcohol, deionized water are mixed by certain volume ratio, then positive silicic acid is added in magnetic agitation 48min Ethyl ester is heated and is stirred to react, is cooled to room temperature after the reaction was completed, is washed repeatedly using ethyl alcohol and deionized water, true at 56 DEG C The dry 11h of sky is made particle size and is distributed controllable SiO2Particle；The parts by volume of each raw material is, 0.8 parts by volume of ammonium hydroxide, 78.8 parts by volume of ethyl alcohol, 17 parts by volume of deionized water, 3.4 parts by volume of ethyl orthosilicate；Reaction temperature is 60 DEG C, time 3h；
(2) deionized water is heated to 78 DEG C, is gradually added into Lauxite and glucose under stirring, until the two is no longer Dissolution, is filtered to remove undissolved part, obtains mixing saturated solution；
(3) by SiO2Particle is added in mixing saturated solution, is first dispersed with stirring 26min, then delays temperature under stirring Slowly 14 DEG C are down to, Lauxite and glucose moiety are precipitated and are coated on SiO2Particle surface, filtering, obtains Lauxite and Portugal Grape sugar is shell, SiO2For the compound particle of core；The parts by weight of each raw material are SiO237 parts by weight of particle, mixing 63 weight of saturated solution Measure part；Cooling rate is 2 DEG C/min；
(4) compound particle that step (3) obtains is placed in vacuum tube furnace, is passed through nitrogen, then with the speed liter of 4 DEG C/min Temperature keeps the temperature 2.5h to 670 DEG C, so that Lauxite and glucose is carbonized, takes out after cooling, and it is shell, SiO that N doping carbon-coating, which is made,2 For the compound particle of core；
(5) compound particle that step (4) obtains is placed in sodium hydroxide solution, 2h is impregnated at 76 DEG C and removes SiO2Kernel, Then it cools down, be filtered, washed to neutrality, be dried in vacuo 5h at 87 DEG C, hollow nitrogen-doped carbon particle is made；Sodium hydroxide solution Molar concentration is 1mol/L；
(6) hollow nitrogen-doped carbon particle, nanometer polythiophene are added in deionized water and stir 28min, hydroxide is then added Lithium, cobalt carbonate, ammonium phosphate simultaneously stir 16min, are transferred in hydrothermal reaction kettle and are reacted, and take out after cooling, filter, wash, 11h is dried in vacuo at 56 DEG C, obtained N doping carbon-coating is shell, the composite particles that polythiophene doping phosphoric acid cobalt lithium is core, i.e. lithium electricity Pond size tunable cobalt phosphate lithium composite positive pole；The parts by weight of each raw material are that hollow 4 parts by weight of nitrogen-doped carbon particle are received 1 parts by weight of rice polythiophene, 5 parts by weight of lithium hydroxide, 16 parts by weight of cobalt carbonate, 20 parts by weight of ammonium phosphate, 54 weight of deionized water Part；The average grain diameter of nanometer polythiophene is 16nm；The temperature of hydro-thermal reaction is 176 DEG C, time 9h.
Embodiment 2
(1) ammonium hydroxide, ethyl alcohol, deionized water are mixed by certain volume ratio, then positive silicic acid is added in magnetic agitation 45min Ethyl ester is heated and is stirred to react, is cooled to room temperature after the reaction was completed, is washed repeatedly using ethyl alcohol and deionized water, true at 52 DEG C The dry 11h of sky is made particle size and is distributed controllable SiO2Particle；The parts by volume of each raw material is, 0.7 parts by volume of ammonium hydroxide, 80.1 parts by volume of ethyl alcohol, 16 parts by volume of deionized water, 3.2 parts by volume of ethyl orthosilicate；Reaction temperature is 55 DEG C, time 3h；
(2) deionized water is heated to 75 DEG C, is gradually added into Lauxite and glucose under stirring, until the two is no longer Dissolution, is filtered to remove undissolved part, obtains mixing saturated solution；
(3) by SiO2Particle is added in mixing saturated solution, is first dispersed with stirring 22min, then delays temperature under stirring Slowly 12 DEG C are down to, Lauxite and glucose moiety are precipitated and are coated on SiO2Particle surface, filtering, obtains Lauxite and Portugal Grape sugar is shell, SiO2For the compound particle of core；The parts by weight of each raw material are SiO236 parts by weight of particle, mixing 64 weight of saturated solution Measure part；Cooling rate is 1 DEG C/min；
(4) compound particle that step (3) obtains is placed in vacuum tube furnace, is passed through nitrogen, then with the speed liter of 3 DEG C/min Temperature keeps the temperature 3h to 660 DEG C, so that Lauxite and glucose is carbonized, takes out after cooling, and it is shell, SiO that N doping carbon-coating, which is made,2For The compound particle of core；
(5) compound particle that step (4) obtains is placed in sodium hydroxide solution, 2.5h is impregnated at 72 DEG C and removes SiO2It is interior Then core is cooled down, is filtered, washed to neutrality, is dried in vacuo 5.5h at 82 DEG C, hollow nitrogen-doped carbon particle is made；Sodium hydroxide The molar concentration of solution is 1mol/L；
(6) hollow nitrogen-doped carbon particle, nanometer polythiophene are added in deionized water and stir 25min, hydroxide is then added Lithium, cobalt carbonate, ammonium phosphate simultaneously stir 12min, are transferred in hydrothermal reaction kettle and are reacted, and take out after cooling, filter, wash, 11.5h is dried in vacuo at 53 DEG C, obtained N doping carbon-coating is shell, the composite particles that polythiophene doping phosphoric acid cobalt lithium is core, i.e. lithium Battery size tunable cobalt phosphate lithium composite positive pole；The parts by weight of each raw material are, hollow 3 parts by weight of nitrogen-doped carbon particle, 1 parts by weight of nanometer polythiophene, 5 parts by weight of lithium hydroxide, 16 parts by weight of cobalt carbonate, 20 parts by weight of ammonium phosphate, 55 weight of deionized water Measure part；The average grain diameter of nanometer polythiophene is 12nm；The temperature of hydro-thermal reaction is 172 DEG C, time 9.5h.
Embodiment 3
(1) ammonium hydroxide, ethyl alcohol, deionized water are mixed by certain volume ratio, then positive silicic acid is added in magnetic agitation 55min Ethyl ester is heated and is stirred to react, is cooled to room temperature after the reaction was completed, is washed repeatedly using ethyl alcohol and deionized water, true at 58 DEG C The dry 9h of sky is made particle size and is distributed controllable SiO2Particle；The parts by volume of each raw material is 0.9 parts by volume of ammonium hydroxide, second 76.4 parts by volume of alcohol, 19 parts by volume of deionized water, 3.7 parts by volume of ethyl orthosilicate；Reaction temperature is 58 DEG C, time 2h；
(2) deionized water is heated to 85 DEG C, is gradually added into Lauxite and glucose under stirring, until the two is no longer Dissolution, is filtered to remove undissolved part, obtains mixing saturated solution；
(3) by SiO2Particle is added in mixing saturated solution, is first dispersed with stirring 28min, then delays temperature under stirring Slowly 18 DEG C are down to, Lauxite and glucose moiety are precipitated and are coated on SiO2Particle surface, filtering, obtains Lauxite and Portugal Grape sugar is shell, SiO2For the compound particle of core；The parts by weight of each raw material are SiO238 parts by weight of particle, mixing 62 weight of saturated solution Measure part；Cooling rate is 3 DEG C/min；
(4) compound particle that step (3) obtains is placed in vacuum tube furnace, is passed through nitrogen, then with the speed liter of 5 DEG C/min Temperature keeps the temperature 2h to 690 DEG C, so that Lauxite and glucose is carbonized, takes out after cooling, and it is shell, SiO that N doping carbon-coating, which is made,2For The compound particle of core；
(5) compound particle that step (4) obtains is placed in sodium hydroxide solution, 2.5h is impregnated at 72 DEG C and removes SiO2It is interior Then core is cooled down, is filtered, washed to neutrality, is dried in vacuo 5.5h at 82 DEG C, hollow nitrogen-doped carbon particle is made；Sodium hydroxide The molar concentration of solution is 1mol/L；
(6) hollow nitrogen-doped carbon particle, nanometer polythiophene are added in deionized water and stir 25min, hydroxide is then added Lithium, cobalt carbonate, ammonium phosphate simultaneously stir 12min, are transferred in hydrothermal reaction kettle and are reacted, and take out after cooling, filter, wash, 11.5h is dried in vacuo at 52 DEG C, obtained N doping carbon-coating is shell, the composite particles that polythiophene doping phosphoric acid cobalt lithium is core, i.e. lithium Battery size tunable cobalt phosphate lithium composite positive pole；The parts by weight of each raw material are hollow 3.5 weight of nitrogen-doped carbon particle Part, 1 parts by weight of nanometer polythiophene, 4.5 parts by weight of lithium hydroxide, 16 parts by weight of cobalt carbonate, 20 parts by weight of ammonium phosphate, deionized water 55 parts by weight；The average grain diameter of nanometer polythiophene is 12nm；The temperature of hydro-thermal reaction is 173 DEG C, time 9.5h.
Embodiment 4
(1) ammonium hydroxide, ethyl alcohol, deionized water are mixed by certain volume ratio, then positive silicic acid is added in magnetic agitation 40min Ethyl ester is heated and is stirred to react, is cooled to room temperature after the reaction was completed, is washed repeatedly using ethyl alcohol and deionized water, true at 50 DEG C The dry 12h of sky is made particle size and is distributed controllable SiO2Particle；The parts by volume of each raw material is, 0.7 parts by volume of ammonium hydroxide, 81.3 parts by volume of ethyl alcohol, 15 parts by volume of deionized water, 3 parts by volume of ethyl orthosilicate；Reaction temperature is 55 DEG C, time 3h；
(2) deionized water is heated to 70 DEG C, is gradually added into Lauxite and glucose under stirring, until the two is no longer Dissolution, is filtered to remove undissolved part, obtains mixing saturated solution；
(3) by SiO2Particle is added in mixing saturated solution, is first dispersed with stirring 20min, then delays temperature under stirring Slowly 10 DEG C are down to, Lauxite and glucose moiety are precipitated and are coated on SiO2Particle surface, filtering, obtains Lauxite and Portugal Grape sugar is shell, SiO2For the compound particle of core；The parts by weight of each raw material are SiO235 parts by weight of particle, mixing 65 weight of saturated solution Measure part；Cooling rate is 1 DEG C/min；
(4) compound particle that step (3) obtains is placed in vacuum tube furnace, is passed through nitrogen, then with the speed liter of 3 DEG C/min Temperature keeps the temperature 3h to 650 DEG C, so that Lauxite and glucose is carbonized, takes out after cooling, and it is shell, SiO that N doping carbon-coating, which is made,2For The compound particle of core；
(5) compound particle that step (4) obtains is placed in sodium hydroxide solution, 2.5h is impregnated at 70 DEG C and removes SiO2It is interior Then core is cooled down, is filtered, washed to neutrality, is dried in vacuo 6h at 80 DEG C, hollow nitrogen-doped carbon particle is made；Sodium hydroxide is molten The molar concentration of liquid is 1mol/L；
(6) hollow nitrogen-doped carbon particle, nanometer polythiophene are added in deionized water and stir 20min, hydroxide is then added Lithium, cobalt carbonate, ammonium phosphate simultaneously stir 10min, are transferred in hydrothermal reaction kettle and are reacted, and take out after cooling, filter, wash, 12h is dried in vacuo at 50 DEG C, obtained N doping carbon-coating is shell, the composite particles that polythiophene doping phosphoric acid cobalt lithium is core, i.e. lithium electricity Pond size tunable cobalt phosphate lithium composite positive pole；The parts by weight of each raw material are that hollow 3 parts by weight of nitrogen-doped carbon particle are received 1 parts by weight of rice polythiophene, 4 parts by weight of lithium hydroxide, 16 parts by weight of cobalt carbonate, 20 parts by weight of ammonium phosphate, 56 weight of deionized water Part；The average grain diameter of nanometer polythiophene is 10nm；The temperature of hydro-thermal reaction is 170 DEG C, time 10h.
Embodiment 5
(1) ammonium hydroxide, ethyl alcohol, deionized water are mixed by certain volume ratio, then positive silicic acid is added in magnetic agitation 60min Ethyl ester is heated and is stirred to react, is cooled to room temperature after the reaction was completed, is washed repeatedly using ethyl alcohol and deionized water, true at 60 DEG C The dry 8h of sky is made particle size and is distributed controllable SiO2Particle；The parts by volume of each raw material is 0.9 parts by volume of ammonium hydroxide, second 75.1 parts by volume of alcohol, 20 parts by volume of deionized water, 4 parts by volume of ethyl orthosilicate；Reaction temperature is 60 DEG C, time 2h；
(2) deionized water is heated to 90 DEG C, is gradually added into Lauxite and glucose under stirring, until the two is no longer Dissolution, is filtered to remove undissolved part, obtains mixing saturated solution；
(3) by SiO2Particle is added in mixing saturated solution, is first dispersed with stirring 30min, then delays temperature under stirring Slowly 20 DEG C are down to, Lauxite and glucose moiety are precipitated and are coated on SiO2Particle surface, filtering, obtains Lauxite and Portugal Grape sugar is shell, SiO2For the compound particle of core；The parts by weight of each raw material are SiO240 parts by weight of particle, mixing 60 weight of saturated solution Measure part；Cooling rate is 3 DEG C/min；
(4) compound particle that step (3) obtains is placed in vacuum tube furnace, is passed through nitrogen, then with the speed liter of 5 DEG C/min Temperature keeps the temperature 3h to 700 DEG C, so that Lauxite and glucose is carbonized, takes out after cooling, and it is shell, SiO that N doping carbon-coating, which is made,2For The compound particle of core；
(5) compound particle that step (4) obtains is placed in sodium hydroxide solution, 2h is impregnated at 80 DEG C and removes SiO2Kernel, Then it cools down, be filtered, washed to neutrality, be dried in vacuo 4h at 90 DEG C, hollow nitrogen-doped carbon particle is made；Sodium hydroxide solution Molar concentration be 1mol/L；
(6) hollow nitrogen-doped carbon particle, nanometer polythiophene are added in deionized water and stir 40min, hydroxide is then added Lithium, cobalt carbonate, ammonium phosphate simultaneously stir 20min, are transferred in hydrothermal reaction kettle and are reacted, and take out after cooling, filter, wash, 10h is dried in vacuo at 60 DEG C, obtained N doping carbon-coating is shell, the composite particles that polythiophene doping phosphoric acid cobalt lithium is core, i.e. lithium electricity Pond size tunable cobalt phosphate lithium composite positive pole；The parts by weight of each raw material are that hollow 5 parts by weight of nitrogen-doped carbon particle are received 2 parts by weight of rice polythiophene, 6 parts by weight of lithium hydroxide, 16 parts by weight of cobalt carbonate, 20 parts by weight of ammonium phosphate, 51 weight of deionized water Part；The average grain diameter of nanometer polythiophene is 20nm；The temperature of hydro-thermal reaction is 180 DEG C, time 8h.
Embodiment 6
(1) ammonium hydroxide, ethyl alcohol, deionized water are mixed by certain volume ratio, then positive silicic acid is added in magnetic agitation 50min Ethyl ester is heated and is stirred to react, is cooled to room temperature after the reaction was completed, is washed repeatedly using ethyl alcohol and deionized water, true at 55 DEG C The dry 10h of sky is made particle size and is distributed controllable SiO2Particle；The parts by volume of each raw material is, 0.8 parts by volume of ammonium hydroxide, 77.7 parts by volume of ethyl alcohol, 18 parts by volume of deionized water, 3.5 parts by volume of ethyl orthosilicate；Reaction temperature is 58 DEG C, and the time is 2.5h；
(2) deionized water is heated to 80 DEG C, is gradually added into Lauxite and glucose under stirring, until the two is no longer Dissolution, is filtered to remove undissolved part, obtains mixing saturated solution；
(3) by SiO2Particle is added in mixing saturated solution, is first dispersed with stirring 25min, then delays temperature under stirring Slowly 15 DEG C are down to, Lauxite and glucose moiety are precipitated and are coated on SiO2Particle surface, filtering, obtains Lauxite and Portugal Grape sugar is shell, SiO2For the compound particle of core；The parts by weight of each raw material are SiO238 parts by weight of particle, mixing 62 weight of saturated solution Measure part；Cooling rate is 2 DEG C/min；
(4) compound particle that step (3) obtains is placed in vacuum tube furnace, is passed through nitrogen, then with the speed liter of 4 DEG C/min Temperature keeps the temperature 2.5h to 680 DEG C, so that Lauxite and glucose is carbonized, takes out after cooling, and it is shell, SiO that N doping carbon-coating, which is made,2 For the compound particle of core；
(5) compound particle that step (4) obtains is placed in sodium hydroxide solution, 2.5h is impregnated at 75 DEG C and removes SiO2It is interior Then core is cooled down, is filtered, washed to neutrality, is dried in vacuo 5h at 85 DEG C, hollow nitrogen-doped carbon particle is made；Sodium hydroxide is molten The molar concentration of liquid is 1mol/L；
(6) hollow nitrogen-doped carbon particle, nanometer polythiophene are added in deionized water and stir 30min, hydroxide is then added Lithium, cobalt carbonate, ammonium phosphate simultaneously stir 15min, are transferred in hydrothermal reaction kettle and are reacted, and take out after cooling, filter, wash, 11h is dried in vacuo at 55 DEG C, obtained N doping carbon-coating is shell, the composite particles that polythiophene doping phosphoric acid cobalt lithium is core, i.e. lithium electricity Pond size tunable cobalt phosphate lithium composite positive pole；The parts by weight of each raw material are that hollow 4 parts by weight of nitrogen-doped carbon particle are received 2 parts by weight of rice polythiophene, 5 parts by weight of lithium hydroxide, 16 parts by weight of cobalt carbonate, 20 parts by weight of ammonium phosphate, 53 weight of deionized water Part；The average grain diameter of nanometer polythiophene is 15nm；The temperature of hydro-thermal reaction is 175 DEG C, time 9h.
Comparative example 1
It first passes through hydro-thermal method and prepares cobalt phosphate lithium particle, then coated urea-formaldehyde resin and glucose, then high temperature cabonization obtains nitrogen and mixes The composite particles that miscellaneous carbon-coating is shell, cobalt phosphate lithium is core.
Performance test:
(1) it average grain diameter and polydispersity index: takes a certain amount of cobalt phosphate lithium positive electrode produced by the present invention as sample, uses Laser particle size analyzer is tested to obtain the average grain diameter of sample, and retest calculates average value, then calculates the more of particle diameter distribution Dispersion index；
(2) positive plate is made in positive electrode produced by the present invention, using Celgard2400 microporous polypropylene membrane as diaphragm, 1mol/ The LiPF of L6Mixed organic solvents (EC:DMC=1:1, volume ratio) be electrolyte, be that argon is being full of to pole piece with metal lithium sheet It is assembled into the button cell of model CR2025 in the glove box of gas, carries out following test:
Electronic conductivity, ionic conductivity: it after carrying out electrochemistry circulation 1 week using LandCT2001A battery test system, uses Zahner IM6ex type electrochemical workstation measures the electrochemical impedance of material, and measurement frequency range is 10kHz ~ 10mHz, perturbation Voltage is 5mV, tests and calculate the electronic conductivity and ionic conductivity of positive electrode；
Charge and discharge cycles test specific capacity: carrying out charge and discharge cycles test, charging/discharging voltage model using battery performance testing system Enclose for 2 ~ 4V, test respectively under 1C multiplying power for the first time, circulation 50 weeks and 100 weeks charging and discharging capacities of circulation.
The data obtained is as shown in table 1.
Table 1:

Claims (9)

1. a kind of method for preparing lithium battery size tunable cobalt phosphate lithium composite positive pole, which is characterized in that the phosphoric acid Specific step is as follows for the preparation of cobalt lithium composite positive pole:
(1) ammonium hydroxide, ethyl alcohol, deionized water are mixed by certain volume ratio, then positive silicon is added in 40 ~ 60min of magnetic agitation Acetoacetic ester is heated and is stirred to react, is cooled to room temperature after the reaction was completed, is washed repeatedly using ethyl alcohol and deionized water, and 50 ~ 60 DEG C 8 ~ 12h of lower vacuum drying is made particle size and is distributed controllable SiO2Particle；
(2) deionized water is heated to 70 ~ 90 DEG C, is gradually added into Lauxite and glucose under stirring, until the two is It is not redissolved, is filtered to remove undissolved part, obtain mixing saturated solution；
(3) by SiO2Particle is added in mixing saturated solution, 20 ~ 30min is first dispersed with stirring, then by temperature under stirring 10 ~ 20 DEG C are slowly dropped to, Lauxite and glucose moiety are precipitated and are coated on SiO2Particle surface, filtering, obtains ureaformaldehyde tree Rouge and glucose are shell, SiO2For the compound particle of core；
(4) compound particle that step (3) obtains is placed in vacuum tube furnace, is passed through nitrogen, then with the speed of 3 ~ 5 DEG C/min 650 ~ 700 DEG C are warming up to, 2 ~ 3h is kept the temperature, so that Lauxite and glucose is carbonized, is taken out after cooling, obtained N doping carbon-coating is Shell, SiO2For the compound particle of core；
(5) compound particle that step (4) obtains is placed in sodium hydroxide solution, 2 ~ 2.5h is impregnated at 70 ~ 80 DEG C and removes SiO2 Then kernel is cooled down, is filtered, washed to neutrality, 4 ~ 6h is dried in vacuo at 80 ~ 90 DEG C, hollow nitrogen-doped carbon particle is made；
(6) hollow nitrogen-doped carbon particle, nanometer polythiophene are added in deionized water and are stirred 20 ~ 40min, hydrogen-oxygen is then added Change lithium, cobalt carbonate, ammonium phosphate and stir 10 ~ 20min, is transferred in hydrothermal reaction kettle and is reacted, taken out after cooling, filter, It washs, 10 ~ 12h is dried in vacuo at 50 ~ 60 DEG C, obtained N doping carbon-coating is shell, polythiophene doping phosphoric acid cobalt lithium is the compound of core Particle, i.e. lithium battery size tunable cobalt phosphate lithium composite positive pole.
2. a kind of method for preparing lithium battery size tunable cobalt phosphate lithium composite positive pole according to claim 1, Be characterized in that: the parts by volume of step (1) each raw material is that 0.7 ~ 0.9 parts by volume of ammonium hydroxide, is gone at 75.1 ~ 81.3 parts by volume of ethyl alcohol 15 ~ 20 parts by volume of ionized water, 3 ~ 4 parts by volume of ethyl orthosilicate.
3. a kind of method for preparing lithium battery size tunable cobalt phosphate lithium composite positive pole according to claim 1, Be characterized in that: step (1) reaction temperature is 55 ~ 60 DEG C, and the time is 2 ~ 3h.
4. a kind of method for preparing lithium battery size tunable cobalt phosphate lithium composite positive pole according to claim 1, Be characterized in that: the parts by weight of step (3) each raw material are SiO235 ~ 40 parts by weight of particle, mixing 60 ~ 65 weight of saturated solution Measure part.
5. a kind of method for preparing lithium battery size tunable cobalt phosphate lithium composite positive pole according to claim 1, Be characterized in that: step (3) cooling rate is 1 ~ 3 DEG C/min.
6. a kind of method for preparing lithium battery size tunable cobalt phosphate lithium composite positive pole according to claim 1, Be characterized in that: the molar concentration of step (5) described sodium hydroxide solution is 1mol/L.
7. a kind of method for preparing lithium battery size tunable cobalt phosphate lithium composite positive pole according to claim 1, Be characterized in that: the parts by weight of step (6) each raw material are hollow 3 ~ 5 parts by weight of nitrogen-doped carbon particle, nanometer polythiophene 1 ~ 2 Parts by weight, 4 ~ 6 parts by weight of lithium hydroxide, 16 parts by weight of cobalt carbonate, 20 parts by weight of ammonium phosphate, 51 ~ 56 parts by weight of deionized water.
8. a kind of method for preparing lithium battery size tunable cobalt phosphate lithium composite positive pole according to claim 1, Be characterized in that: the partial size of step (6) the nanometer polythiophene is 10 ~ 20nm.
9. a kind of method for preparing lithium battery size tunable cobalt phosphate lithium composite positive pole according to claim 1, Be characterized in that: the temperature of step (6) described hydro-thermal reaction is 170 ~ 180 DEG C, and the time is 8 ~ 10h.
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CN114735796A (en) * 2022-05-16 2022-07-12 湖南工业大学 Iron-based nano flocculant and preparation method and application thereof

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