CN111180716B - Bismuth phosphate positive electrode material with good conductivity for lithium battery and preparation method - Google Patents

Bismuth phosphate positive electrode material with good conductivity for lithium battery and preparation method Download PDF

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CN111180716B
CN111180716B CN202010096277.4A CN202010096277A CN111180716B CN 111180716 B CN111180716 B CN 111180716B CN 202010096277 A CN202010096277 A CN 202010096277A CN 111180716 B CN111180716 B CN 111180716B
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bismuth
lithium
phosphate
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bismuth phosphate
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CN111180716A (en
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蒋涛
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Shenzhen Dehui Cell Material 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
    • 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
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 invention relates to the technical field of lithium battery anode materials, and provides a bismuth phosphate anode material with good conductivity for a lithium battery and a preparation method thereof. The method comprises the steps of firstly preparing a bismuth phosphate precursor and a lithium vanadate precursor respectively, then preparing a nano carbon black suspension, adding the bismuth phosphate precursor and the lithium vanadate precursor into the suspension to obtain a composite wet gel, then carrying out ball milling, and finally carrying out sectional calcination to obtain the lithium vanadate and carbon black composite bismuth phosphate anode material. Compared with bismuth phosphate which is not subjected to composite modification, the conductivity of the bismuth phosphate anode material prepared by the invention is obviously improved.

Description

Bismuth phosphate positive electrode material with good conductivity for lithium battery and preparation method
Technical Field
The invention belongs to the technical field of lithium battery anode materials, and provides a bismuth phosphate anode material with good conductivity for a lithium battery and a preparation method thereof.
Background
The energy density of a lithium battery is closely related to the battery capacity and the electromotive force, and is mainly controlled by the positive electrode capacity. The capacity of the positive electrode is doubled, the energy density of the lithium battery can be improved by 57 percent, the capacity of the negative electrode is improved by ten times, and the energy density of the lithium battery is only increased by 47 percent. Therefore, the main direction for increasing the energy density of lithium batteries is to find better positive electrode materials. The chemical conversion reaction is a novel lithium storage mechanism of the lithium ion battery which is gradually developed in recent years, and the electrode material based on the mechanism breaks through the structural limitation of the traditional embedded compound, so that the multi-electron transfer reaction can be realized in the charge and discharge process, and a new way is provided for the research and development and application of the high-energy-density anode material.
The essence of the chemical conversion reaction is a displacement reaction, and all oxidation states of metal cations in the positive electrode material participate in the reaction and are completely reduced into metal simple substances in the charging and discharging processes, so that the multi-electron reaction is realized. In the structure of bismuth phosphate, since polyanion PO exists4 3-PO by a Bi-O-P inducing effect4 3-In (3) a P-O covalent bond can stabilize Bi3+And the theoretical output voltage is higher in the chemical conversion reaction. The theoretical output voltage of the bismuth phosphate is about 3.1V, the theoretical specific discharge capacity is 265.5mAh/g, the theoretical mass energy density is 830.5Wh/kg, and the theoretical volume energy density is 5253.1 Wh/L. Therefore, the bismuth phosphate can be used as an ideal choice for the positive electrode material of the chemical conversion reaction lithium battery. However, bismuth phosphate has poor conductivityIt is a drawback of the positive electrode material. In order to obtain an ideal bismuth phosphate cathode material, bismuth phosphate needs to be modified to improve the conductivity.
Disclosure of Invention
It can be seen that the bismuth phosphate of the prior art has the disadvantage of poor conductivity when used as a positive electrode material for lithium batteries. Aiming at the situation, the invention provides a bismuth phosphate anode material with good conductivity for a lithium battery and a preparation method thereof, and the purpose of obviously improving the conductivity of bismuth phosphate is achieved.
In order to achieve the purpose, the invention relates to the following specific technical scheme:
a preparation method of a bismuth phosphate positive electrode material with good conductivity for a lithium battery comprises the following steps:
(1) adding a bismuth source into dilute nitric acid, and stirring at room temperature until the bismuth source is completely dissolved to obtain a bismuth source solution; adding a phosphorus source into deionized water, and stirring at room temperature until the phosphorus source is completely dissolved to obtain a phosphorus source solution; adding o-dichlorobenzene into the bismuth source solution, performing ultrasonic dispersion for 20-30min, adding the phosphorus source solution, dropwise adding a phosphoric acid solution to adjust the pH value to 2-3, placing in a constant-temperature water bath at 40-50 ℃, performing ultrasonic oscillation for 30-50min, performing suction filtration, and washing to obtain a bismuth phosphate precursor;
(2) adding a lithium source and ammonium vanadate into deionized water, ultrasonically oscillating for 20-30min, then dropwise adding ammonia water to adjust the pH value to 8.5, heating to boil, reacting for 40-60min, and then performing suction filtration and washing to obtain a lithium vanadate precursor;
(3) adding the nano carbon black and sodium dodecyl benzene sulfonate into deionized water, and performing ultrasonic dispersion for 20-30min to obtain a suspension; adding a bismuth phosphate precursor and a lithium vanadate precursor into the suspension, continuing to perform ultrasonic dispersion for 40-60min, and heating to evaporate part of water to obtain a composite wet gel;
(4) and under the protection of nitrogen, placing the composite wet gel in a planetary ball mill for wet ball milling, then placing the composite wet gel in a muffle furnace, firstly calcining for 2-3h at the temperature of 200-220 ℃, and then calcining for 1-2h at the temperature of 300-350 ℃ to obtain the bismuth phosphate/lithium vanadate/carbon black composite material, namely the bismuth phosphate anode material with good electrical conductivity for the lithium battery.
Preferably, the bismuth source is one or two of bismuth nitrate pentahydrate and bismuth sulfate heptahydrate.
Preferably, the phosphorus source is one or more of sodium phosphate, potassium phosphate and ammonium phosphate.
Preferably, the dilute nitric acid has a pH of 2.
Preferably, the lithium source is one or two of lithium carbonate and lithium hydroxide.
Preferably, in the step (1), the molar concentration of the bismuth source in the bismuth source solution is 0.1-0.2 mol/L.
Preferably, in the step (1), the molar concentration of the phosphorus source in the phosphorus source solution is 0.1-0.15 mol/L.
Preferably, in the step (1), the molar ratio of Bi and P in the bismuth source and the phosphorus source is 1: 1.
preferably, in the step (1), the molar ratio of the o-dichlorobenzene to the phosphorus source is 0.03-0.05: 1.
preferably, in the step (2), the molar concentration of the ammonium vanadate in the deionized water is 0.3-0.5 mol/L.
Preferably, in the step (2), the molar ratio of Li to V in the lithium source and the ammonium vanadate is 1: 3.
preferably, in the step (3), by weight, 20-25 parts of a bismuth phosphate precursor, 4-8 parts of a lithium vanadate precursor, 0.5-0.8 part of nano carbon black, 0.05-0.1 part of sodium dodecyl benzene sulfonate and 100 parts of deionized water.
Preferably, in the step (3), the moisture content of the composite wet gel is 55%.
Preferably, in the step (4), the revolution speed of the ball mill is 200-.
The invention also provides a bismuth phosphate anode material with good conductivity for the lithium battery, which is prepared by the preparation method, and the anode material is formed by compounding bismuth phosphate, lithium vanadate and nano carbon black. Through compounding with lithium vanadate and nano carbon black, the electronic conductivity of a bismuth phosphate positive electrode material sample can be adjusted from 2.2 multiplied by 10-5The S/cm rises to 5.7X 10-2-7.8×10-2S/cm, the conductivity of the bismuth phosphate is obviously improved.
The invention provides a bismuth phosphate anode material with good conductivity for a lithium battery and a preparation method thereof, and the bismuth phosphate anode material has the beneficial effects that:
1. according to the preparation method, lithium vanadate and bismuth phosphate are compounded, the lithium vanadate has high specific capacity, and is charged and discharged through reversible intercalation and deintercalation reactions of lithium ions: charge transfer occurs during lithium ion intercalation, and electrons are transferred from Li to V5+，LiV3O8Conversion to Li2V3O8、Li3V3O8、Li4V3O8Three V5+Reduction may occur to varying degrees; opposite charge transfer occurs during lithium ion deintercalation, Li2V3O8、Li3V3O8、Li4V3O8Delithiation to LiV3O8Electrons from V4 +Transfer to Li+. According to the invention, lithium vanadate based on an intercalation reaction mechanism is compounded with bismuth phosphate based on a chemical conversion reaction, and during charging and discharging, charge transfer generated by the lithium vanadate can improve the conductivity of the bismuth phosphate.
2. According to the preparation method, the nano carbon black and the bismuth phosphate are compounded, and the carbon black with good conductivity is utilized to form a conductive connection point in the bismuth phosphate, so that the purpose of further improving the conductivity of the bismuth phosphate is achieved.
3. According to the preparation method, the bismuth phosphate, the lithium vanadate and the nano carbon black are subjected to mixed ball milling, and the bismuth phosphate and the lithium vanadate particles are in close contact with the carbon black, so that the growth of the bismuth phosphate and the lithium vanadate particles can be limited, the particles with smaller particle size can be obtained, the lithium ion diffusion path is shorter, the lithium intercalation amount of lithium vanadate intercalation reaction can be increased, the chemical conversion reaction efficiency of bismuth phosphate can be improved, and the charge transfer efficiency can be improved, so that the conductivity of the material can be improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Adding 1mol of pentahydrate bismuth nitrate into 6.7L of dilute nitric acid with the pH value of 2, and stirring at room temperature until the bismuth nitrate is completely dissolved to obtain a bismuth source solution; adding 1mol of ammonium phosphate into 8.3L of deionized water, and stirring at room temperature until the ammonium phosphate is completely dissolved to obtain a phosphorus source solution; adding 0.03mol of o-dichlorobenzene into the bismuth source solution, performing ultrasonic dispersion for 30min, adding the phosphorus source solution, dropwise adding a phosphoric acid solution to adjust the pH value to be 2, placing in a constant-temperature water bath at 50 ℃, performing ultrasonic oscillation for 30min, performing suction filtration and washing to obtain a bismuth phosphate precursor;
(2) adding 0.133mol of lithium hydroxide and 0.4mol of ammonium vanadate into 1L of deionized water, ultrasonically oscillating for 30min, then dropwise adding ammonia water to adjust the pH value to 8.5, heating to boil, and carrying out suction filtration and washing after reacting for 40min to obtain a lithium vanadate precursor;
(3) adding 0.5 part by weight of nano carbon black and 0.1 part by weight of sodium dodecyl benzene sulfonate into 100 parts by weight of deionized water, and performing ultrasonic dispersion for 20min to obtain a suspension; adding 25 parts by weight of bismuth phosphate precursor and 4 parts by weight of lithium vanadate precursor into the suspension, continuing to perform ultrasonic dispersion for 40min, and heating to evaporate part of water to obtain composite wet gel with the water content of 55%;
(4) and under the protection of nitrogen, placing the composite wet gel in a planetary ball mill, setting the revolution speed of the ball mill to be 200r/min and the rotation speed to be 400r/min, carrying out ball milling for 2h, then placing the composite wet gel in a muffle furnace, firstly calcining for 2h at 220 ℃, and then calcining for 2h at 350 ℃ to obtain the bismuth phosphate/lithium vanadate/carbon black composite material, namely the bismuth phosphate anode material with good conductivity for the lithium battery.
Example 2
(1) Adding 1mol of pentahydrate bismuth nitrate into 6.7L of dilute nitric acid with the pH value of 2, and stirring at room temperature until the bismuth nitrate is completely dissolved to obtain a bismuth source solution; adding 1mol of potassium phosphate into 8.3L of deionized water, and stirring at room temperature until the potassium phosphate is completely dissolved to obtain a phosphorus source solution; adding 0.05mol of o-dichlorobenzene into the bismuth source solution, performing ultrasonic dispersion for 20min, adding the phosphorus source solution, dropwise adding a phosphoric acid solution to adjust the pH value to 3, placing in a constant-temperature water bath at 40 ℃, performing ultrasonic oscillation for 30min, performing suction filtration and washing to obtain a bismuth phosphate precursor;
(2) adding 0.05mol of lithium carbonate and 0.3mol of ammonium vanadate into 1L of deionized water, carrying out ultrasonic oscillation for 20min, then dropwise adding ammonia water to adjust the pH value to 8.5, heating to boiling, carrying out suction filtration and washing after reacting for 60min, and obtaining a lithium vanadate precursor;
(3) adding 0.6 weight part of nano carbon black and 0.1 weight part of sodium dodecyl benzene sulfonate into 100 weight parts of deionized water, and performing ultrasonic dispersion for 20min to obtain a suspension; adding 25 parts by weight of bismuth phosphate precursor and 5 parts by weight of lithium vanadate precursor into the suspension, continuing to perform ultrasonic dispersion for 60min, and heating to evaporate part of water to obtain composite wet gel with the water content of 55%;
(4) and under the protection of nitrogen, placing the composite wet gel in a planetary ball mill, setting the revolution speed of the ball mill to be 250r/min and the rotation speed to be 500r/min, carrying out ball milling for 2h, then placing the composite wet gel in a muffle furnace, firstly calcining for 3h at 200 ℃, and then calcining for 2h at 300 ℃ to obtain the bismuth phosphate/lithium vanadate/carbon black composite material, namely the bismuth phosphate anode material with good conductivity for the lithium battery.
Example 3
(1) Adding 0.5mol of bismuth sulfate heptahydrate into 3.3L of dilute nitric acid with the pH value of 2, and stirring at room temperature until the bismuth source solution is completely dissolved to obtain a bismuth source solution; adding 1mol of sodium phosphate into 7L of deionized water, and stirring at room temperature until the sodium phosphate is completely dissolved to obtain a phosphorus source solution; adding 0.04mol of o-dichlorobenzene into the bismuth source solution, performing ultrasonic dispersion for 25min, adding the phosphorus source solution, dropwise adding a phosphoric acid solution to adjust the pH value to 3, placing in a 45 ℃ constant-temperature water bath, performing ultrasonic oscillation for 40min, performing suction filtration and washing to obtain a bismuth phosphate precursor;
(2) adding 0.1mol of lithium hydroxide and 0.3mol of ammonium vanadate into 1L of deionized water, ultrasonically oscillating for 25min, then dropwise adding ammonia water to adjust the pH value to 8.5, heating to boil, reacting for 50min, and then performing suction filtration and washing to obtain a lithium vanadate precursor;
(3) adding 0.7 weight part of nano carbon black and 0.05 weight part of sodium dodecyl benzene sulfonate into 100 weight parts of deionized water, and performing ultrasonic dispersion for 25min to obtain a suspension; adding 23 parts by weight of bismuth phosphate precursor and 6 parts by weight of lithium vanadate precursor into the suspension, continuing to perform ultrasonic dispersion for 50min, and heating to evaporate part of water to obtain composite wet gel with the water content of 55%;
(4) and under the protection of nitrogen, placing the composite wet gel in a planetary ball mill, setting the revolution speed of the ball mill to be 220r/min and the rotation speed to be 440r/min, carrying out ball milling for 2h, then placing the composite wet gel in a muffle furnace, firstly calcining for 2h at 210 ℃, and then calcining for 1h at 350 ℃ to obtain the bismuth phosphate/lithium vanadate/carbon black composite material, namely the bismuth phosphate anode material with good conductivity for the lithium battery.
Example 4
(1) Adding 1mol of pentahydrate bismuth nitrate into 5.5L of dilute nitric acid with the pH value of 2, and stirring at room temperature until the bismuth nitrate is completely dissolved to obtain a bismuth source solution; adding 1mol of ammonium phosphate into 10L of deionized water, and stirring at room temperature until the ammonium phosphate is completely dissolved to obtain a phosphorus source solution; adding 0.04mol of o-dichlorobenzene into the bismuth source solution, performing ultrasonic dispersion for 22min, adding the phosphorus source solution, dropwise adding a phosphoric acid solution to adjust the pH value to be 2, placing in a constant-temperature water bath at 48 ℃, performing ultrasonic oscillation for 35min, performing suction filtration and washing to obtain a bismuth phosphate precursor;
(2) adding 0.067mol of lithium carbonate and 0.4mol of ammonium vanadate into 1L of deionized water, carrying out ultrasonic oscillation for 28min, then dropwise adding ammonia water to adjust the pH value to 8.5, heating to boiling, carrying out suction filtration and washing after reacting for 45min, and obtaining a lithium vanadate precursor;
(3) adding 0.7 weight part of nano carbon black and 0.08 weight part of sodium dodecyl benzene sulfonate into 100 weight parts of deionized water, and performing ultrasonic dispersion for 22min to obtain a suspension; adding 23 parts by weight of bismuth phosphate precursor and 7 parts by weight of lithium vanadate precursor into the suspension, continuing to perform ultrasonic dispersion for 55min, and heating to evaporate part of water to obtain composite wet gel with the water content of 55%;
(4) and under the protection of nitrogen, placing the composite wet gel in a planetary ball mill, setting the revolution speed of the ball mill to be 240r/min and the rotation speed to be 480r/min, carrying out ball milling for 3h, then placing the composite wet gel in a muffle furnace, firstly calcining for 2.5h at 220 ℃, and then calcining for 1.5h at 320 ℃ to obtain the bismuth phosphate/lithium vanadate/carbon black composite material, namely the bismuth phosphate anode material with good conductivity for the lithium battery.
Example 5
(1) Adding 0.5mol of bismuth sulfate heptahydrate into 5L of dilute nitric acid with the pH value of 2, and stirring at room temperature until the bismuth source solution is completely dissolved to obtain a bismuth source solution; adding 1mol of potassium phosphate into 8L of deionized water, and stirring at room temperature until the potassium phosphate is completely dissolved to obtain a phosphorus source solution; adding 0.03mol of o-dichlorobenzene into the bismuth source solution, performing ultrasonic dispersion for 25min, adding the phosphorus source solution, dropwise adding a phosphoric acid solution to adjust the pH value to 3, placing in a constant-temperature water bath at 40 ℃, performing ultrasonic oscillation for 40min, performing suction filtration and washing to obtain a bismuth phosphate precursor;
(2) adding 0.083mol of lithium carbonate and 0.5mol of ammonium vanadate into 1L of deionized water, ultrasonically oscillating for 20min, then dropwise adding ammonia water to adjust the pH value to 8.5, heating to boil, reacting for 60min, and then performing suction filtration and washing to obtain a lithium vanadate precursor;
(3) adding 0.8 part by weight of nano carbon black and 0.06 part by weight of sodium dodecyl benzene sulfonate into 100 parts by weight of deionized water, and performing ultrasonic dispersion for 30min to obtain a suspension; adding 23 parts by weight of bismuth phosphate precursor and 8 parts by weight of lithium vanadate precursor into the suspension, continuing to perform ultrasonic dispersion for 40min, and heating to evaporate part of water to obtain composite wet gel with the water content of 55%;
(4) and under the protection of nitrogen, placing the composite wet gel in a planetary ball mill, setting the revolution speed of the ball mill to be 200r/min and the rotation speed to be 400r/min, carrying out ball milling for 2.5h, then placing the composite wet gel in a muffle furnace, firstly calcining for 2h at 200 ℃, and then calcining for 1h at 350 ℃ to obtain the bismuth phosphate/lithium vanadate/carbon black composite material, namely the bismuth phosphate anode material with good conductivity for the lithium battery.
Example 6
(1) Adding 1mol of bismuth nitrate pentahydrate into 10L of dilute nitric acid with the pH value of 2, and stirring at room temperature until the bismuth nitrate pentahydrate is completely dissolved to obtain a bismuth source solution; adding 1mol of sodium phosphate into 10L of deionized water, and stirring at room temperature until the sodium phosphate is completely dissolved to obtain a phosphorus source solution; adding 0.04mol of o-dichlorobenzene into the bismuth source solution, performing ultrasonic dispersion for 25min, adding the phosphorus source solution, dropwise adding a phosphoric acid solution to adjust the pH value to be 2, placing in a constant-temperature water bath at 50 ℃, performing ultrasonic oscillation for 42min, performing suction filtration and washing to obtain a bismuth phosphate precursor;
(2) adding 0.05mol of lithium carbonate and 0.3mol of ammonium vanadate into 1L of deionized water, carrying out ultrasonic oscillation for 20min, then dropwise adding ammonia water to adjust the pH value to 8.5, heating to boiling, carrying out suction filtration and washing after reacting for 60min, and obtaining a lithium vanadate precursor;
(3) adding 0.8 part by weight of nano carbon black and 0.1 part by weight of sodium dodecyl benzene sulfonate into 100 parts by weight of deionized water, and performing ultrasonic dispersion for 30min to obtain a suspension; adding 20 parts by weight of bismuth phosphate precursor and 8 parts by weight of lithium vanadate precursor into the suspension, continuing to perform ultrasonic dispersion for 60min, and heating to evaporate part of water to obtain composite wet gel with the water content of 55%;
(4) and under the protection of nitrogen, placing the composite wet gel in a planetary ball mill, setting the revolution speed of the ball mill to be 250r/min and the rotation speed to be 500r/min, carrying out ball milling for 2h, then placing the composite wet gel in a muffle furnace, firstly calcining for 3h at 200 ℃, and then calcining for 2h at 300 ℃ to obtain the bismuth phosphate/lithium vanadate/carbon black composite material, namely the bismuth phosphate anode material with good conductivity for the lithium battery.
Comparative example 1
(1) Adding 1mol of bismuth nitrate pentahydrate into 10L of dilute nitric acid with the pH value of 2, and stirring at room temperature until the bismuth nitrate pentahydrate is completely dissolved to obtain a bismuth source solution; adding 1mol of sodium phosphate into 10L of deionized water, and stirring at room temperature until the sodium phosphate is completely dissolved to obtain a phosphorus source solution; adding 0.04mol of o-dichlorobenzene into the bismuth source solution, performing ultrasonic dispersion for 25min, adding the phosphorus source solution, dropwise adding a phosphoric acid solution to adjust the pH value to be 2, placing in a constant-temperature water bath at 50 ℃, performing ultrasonic oscillation for 42min, performing suction filtration and washing to obtain a bismuth phosphate precursor;
(2) under the protection of nitrogen, the bismuth phosphate precursor is placed in a planetary ball mill, the revolution speed of the ball mill is set to be 250r/min, the rotation speed of the ball mill is set to be 500r/min, the ball milling is carried out for 2 hours, then the bismuth phosphate precursor is placed in a muffle furnace, the bismuth phosphate precursor is firstly calcined at 200 ℃ for 3 hours, and then the bismuth phosphate precursor is calcined at 300 ℃ for 2 hours, so that the bismuth phosphate anode material is obtained.
And (3) performance testing: the positive electrode materials obtained in examples 1 to 6 and comparative example 1 were formed into cylindrical sheets having a diameter of 10mm, and the electron conductivity of the samples was measured and calculated at room temperature by the four-probe method, and the obtained data are shown in table 1.
Table 1:
Figure DEST_PATH_IMAGE002

Claims (10)

1. a preparation method of a bismuth phosphate positive electrode material with good conductivity for a lithium battery is characterized by comprising the following steps:
(1) adding a bismuth source into dilute nitric acid, and stirring at room temperature until the bismuth source is completely dissolved to obtain a bismuth source solution; adding a phosphorus source into deionized water, and stirring at room temperature until the phosphorus source is completely dissolved to obtain a phosphorus source solution; adding o-dichlorobenzene into the bismuth source solution, performing ultrasonic dispersion for 20-30min, adding the phosphorus source solution, dropwise adding a phosphoric acid solution to adjust the pH value to 2-3, placing in a constant-temperature water bath at 40-50 ℃, performing ultrasonic oscillation for 30-50min, performing suction filtration, and washing to obtain a bismuth phosphate precursor;
(2) adding a lithium source and ammonium vanadate into deionized water, ultrasonically oscillating for 20-30min, then dropwise adding ammonia water to adjust the pH value to 8.5, heating to boil, reacting for 40-60min, and then performing suction filtration and washing to obtain a lithium vanadate precursor;
(3) adding the nano carbon black and sodium dodecyl benzene sulfonate into deionized water, and performing ultrasonic dispersion for 20-30min to obtain a suspension; adding a bismuth phosphate precursor and a lithium vanadate precursor into the suspension, continuing to perform ultrasonic dispersion for 40-60min, and heating to evaporate part of water to obtain a composite wet gel;
(4) and under the protection of nitrogen, placing the composite wet gel in a planetary ball mill for wet ball milling, then placing the composite wet gel in a muffle furnace, firstly calcining for 2-3h at the temperature of 200-220 ℃, and then calcining for 1-2h at the temperature of 300-350 ℃ to obtain the bismuth phosphate/lithium vanadate/carbon black composite material, namely the bismuth phosphate anode material with good electrical conductivity for the lithium battery.
2. The method of claim 1, wherein the method comprises the steps of: the bismuth source is one or two of bismuth nitrate pentahydrate and bismuth sulfate heptahydrate; the phosphorus source is one or more of sodium phosphate, potassium phosphate and ammonium phosphate; the pH value of the dilute nitric acid is 2; the lithium source is one or two of lithium carbonate and lithium hydroxide.
3. The method of claim 1, wherein the method comprises the steps of: in the step (1), the molar concentration of the bismuth source in the bismuth source solution is 0.1-0.2 mol/L; the molar concentration of the phosphorus source in the phosphorus source solution is 0.1-0.15 mol/L.
4. The method of claim 1, wherein the method comprises the steps of: in the step (1), the molar ratio of Bi to P in the bismuth source and the phosphorus source is 1: 1.
5. the method of claim 1, wherein the method comprises the steps of: in the step (1), the molar ratio of the o-dichlorobenzene to the phosphorus source is 0.03-0.05: 1.
6. the method of claim 1, wherein the method comprises the steps of: in the step (2), the molar concentration of the ammonium vanadate in deionized water is 0.3-0.5 mol/L; the molar ratio of Li to V in the lithium source and ammonium vanadate is 1: 3.
7. the method of claim 1, wherein the method comprises the steps of: in the step (3), by weight, 20-25 parts of a bismuth phosphate precursor, 4-8 parts of a lithium vanadate precursor, 0.5-0.8 part of nano carbon black, 0.05-0.1 part of sodium dodecyl benzene sulfonate and 100 parts of deionized water.
8. The method of claim 1, wherein the method comprises the steps of: in the step (3), the moisture content of the composite wet gel is 55%.
9. The method of claim 1, wherein the method comprises the steps of: in the step (4), the revolution rotating speed of the ball mill is 200-250r/min, the rotation rotating speed is 2 times of the revolution rotating speed, and the ball milling time is 2-3 h.
10. A bismuth phosphate positive electrode material with good conductivity for a lithium battery prepared by the preparation method as set forth in any one of claims 1 to 9, characterized in that: the cathode material is formed by compounding bismuth phosphate, lithium vanadate and nano carbon black.
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