CN108134059B - Negative active material for low-temperature lithium battery and preparation method thereof - Google Patents

Negative active material for low-temperature lithium battery and preparation method thereof Download PDF

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CN108134059B
CN108134059B CN201711384342.8A CN201711384342A CN108134059B CN 108134059 B CN108134059 B CN 108134059B CN 201711384342 A CN201711384342 A CN 201711384342A CN 108134059 B CN108134059 B CN 108134059B
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陈庆
廖健淞
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Shandong Yiwei New Material Co.,Ltd.
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    • H01—ELECTRIC ELEMENTS
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    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01—ELECTRIC ELEMENTS
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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Abstract

The invention provides a negative active material for a low-temperature lithium battery and a preparation method thereof. The surfaces of the metal and the metal oxide are fluorinated to form a metal-fluorine-based net porous structure, so that the corrosion and passivation of electrolyte on a negative electrode material in the lithium deintercalation process are reduced, a deintercalation channel is provided for lithium ions, the electrolyte is decomposed on the surfaces of active material particles in the low-temperature discharge process, and a layer of organic Solid Electrolyte Interface (SEI) film is formed on the surfaces. The structure of the negative active material of the lithium ion battery is basically kept stable in the charging and discharging processes.

Description

Negative active material for low-temperature lithium battery and preparation method thereof
Technical Field
The invention relates to the field of lithium battery cathode materials, in particular to a cathode active material for a low-temperature lithium battery and a preparation method thereof.
Background
The research process of the lithium ion battery cathode material mainly goes through four generations. Metallic lithium is a first-generation cathode material, has high specific capacity, but has active property, so that lithium dendrite can be generated in the charging and discharging process, and a diaphragm is easy to puncture, so that the safety problems of short circuit, electric leakage and the like are caused. The second generation of aluminum-lithium alloy can effectively avoid the problem of lithium dendrite, but after several times of charge-discharge cycles, the material can have serious volume change to cause the powdering of the battery material, so that the structure of the battery is damaged, and the cycle life is low. Improved anode materials of the oxide type have subsequently emerged, but such materials still have drawbacks. After 1980, it was gradually found that, as guided by the Armand theory, when lithium is intercalated into a carbon material, the electrode potential is very close to the potential of lithium metal itself and does not readily react with the organic electrolyte used, so that the cycle performance becomes good. This is the third generation of cathode materials that are currently in widespread use and commercialization. The reversible capacity of the graphite negative electrode material is 300-360 mAh/g. However, with the demand of the battery market, the attention of researchers has been paid and great progress has been made by the new materials with high specific capacity, excellent cycle performance and good safety, which is the fourth generation negative electrode material, i.e. silicon, tin-based and oxide-based negative electrode materials.
The lithium ion battery has the advantages of higher working voltage and energy density, long cycle life, environmental friendliness and the like, and is widely applied to production and life. With the development of modern society, the requirements on electrical appliances are higher and higher. Batteries for small electric appliances such as mobile phones and cameras are gradually developed in the direction of light weight, thinness, long standby time and high safety, while batteries for electric tools, electric bicycles and electric automobiles require higher energy density and safety. The performance of the electrode material directly determines the energy density and safety of the lithium ion battery, so that the development of a high-performance negative electrode material is very important. The carbon material is a current commercial negative electrode material, has the advantages of good conductivity, stable structure, low price and easy obtaining, but has lower specific capacity, and is easy to generate lithium dendrite to cause poor safety. The metal-based negative electrode material and the transition metal oxide have a series of advantages of high theoretical specific capacity, low lithium intercalation potential, rich raw material resources, safety, environmental protection and the like, but the materials are seriously expanded in the lithium intercalation/deintercalation process, so that the materials are easily powdered, and the structure of the battery is finally damaged. By constructing a metal (metal oxide) composite system, a metal or transition metal oxide is dispersed on a carbon material (graphite, carbon nanotube) matrix. The metal with serious volume effect and the oxide thereof are supported by using carbon materials (graphite and carbon nano tubes) so as to relieve volume expansion, improve the electrochemical performance of the cathode material and improve the stability.
In the prior art, graphite is generally used as a negative active material, has the advantages of high specific capacity, flat charge-discharge curve, low price and the like, is an ideal negative material of a lithium ion battery, but has the defects of low first charge-discharge efficiency, poor cycle performance, high selectivity to electrolyte and the like, and the discharge effect of graphite is not ideal in a low-temperature state.
Patent application No. CN2012103090617 discloses a carbon negative electrode material of a lithium ion battery, which takes graphite as a core, pyrolytic carbon as a coating raw material and carbon nanotubes are doped in the coating process.
Disclosure of Invention
Aiming at the defect of unstable low-temperature discharge effect of the conventional lithium ion battery cathode material, the invention provides a preparation method of a cathode active material for a low-temperature lithium battery. The invention is realized by the following technical scheme.
A preparation method of a negative active material for a low-temperature lithium battery comprises the following steps:
(1) mixing metal and its oxide with lithium hydride according to the mass ratio of (2-8) to (1-4) to (0.1-3);
(2) ball-milling the mixed powder in an inert gas atmosphere to obtain a metal and an oxide/lithium hydride composite material thereof;
(3) uniformly mixing metal and oxide thereof/lithium hydride composite material with a fluorine-containing compound according to the mass ratio of 100 (0.5-5), and grinding after mixing;
(4) carrying out heat treatment on the material ground in the step (3) at the temperature of 200-800 ℃ for 1-5 hours to obtain a composite material with a metal-fluorine-based net-shaped porous structure on the surface;
(5) putting the composite material with the metal-fluorine-based net-shaped porous structure on the surface, the hydroxyl organic polymer and the carboxylic acid in the mass ratio of (1-5): 1:1 into a high-pressure reaction kettle, adding a polar solvent into the reaction kettle, violently stirring and dissolving, heating to 100-200 ℃, reacting for 1-60 hours to obtain a metal and an oxide/lithium hydride coordination polymer precursor thereof, washing and drying the product for later use;
(6) and putting the metal and the oxide thereof/lithium hydride coordination polymer precursor into a tubular furnace with inert gas, heating to 200-800 ℃, and reacting for 1-10 hours to obtain the negative active material for the low-temperature lithium battery.
In the scheme, the ball milling speed is 300-500 r/min, the ball milling time is 1-30 hours, the pressure is 1-10 MPa, the temperature is 60-80 ℃, and the particle size of the metal and oxide powder after ball milling is 1-100 mu m.
In the above scheme, the metal and its oxide is one of magnesium and its oxide, cobalt and its oxide, aluminum and its oxide, germanium and its oxide, tin and its oxide, lead and its oxide, antimony and its oxide, gallium and its oxide, cadmium and its oxide, silver and its oxide, manganese and its oxide, molybdenum and its oxide, vanadium and its oxide.
In the above scheme, the fluorine-containing compound is NH4F、NH4PF6、（NH4）3AlF6、NH4BF4One or more of them.
In the above scheme, the hydroxyl organic polymer is one of polyvinyl alcohol, polyethylene glycol, and hydroxyl-terminated polybutadiene.
In the above scheme, the carboxylic acid is one of polyacrylic acid and aromatic acid.
In the above scheme, the inert gas is argon.
In the scheme, the polar solvent is one or more of water, methanol, ethanol, N-dimethylformamide and N, N-dimethylacetamide.
The negative active material for a low-temperature lithium battery is prepared by the method.
The invention has the beneficial effects that: the mass specific capacity of the transformation type transition metal and the oxide thereof is higher, generally 600-1400 mAh/g, and Li formed after lithium intercalation2And O has reversible electrochemical activity, the surface of the O forms a metal-fluorine-based net porous structure after fluorination treatment, the corrosion passivation of electrolyte on a negative electrode material in the lithium de-intercalation process is reduced, a de-intercalation channel is provided for lithium ions, then hydroxyl and carboxyl are grafted on the surface of the O to obtain a metal and oxide coordination organic polymer precursor thereof, the co-intercalation of an organic solvent in the lithium de-intercalation process is further reduced, the interface impedance between the negative electrode and the electrolyte is reduced, the electrolyte decomposition occurs on the surface of the active material particles in the low-temperature discharge process, and a layer of organic solid electrolyte membrane (SEI membrane) is formed on the surface. The structure of the negative active material of the lithium ion battery is basically stable in the charging and discharging processes, the structural damage caused by the back-and-forth expansion of the structure of the lithium ion battery in the charging and discharging cycle is avoided, the low-temperature cycle performance of the negative active material is further improved, the service life of the negative active material is prolonged, the negative active material has better cycle performance than the carbon negative material, and the negative active material can still keep stable after being cycled for thousands of timesThe fixed capacity.
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
Step 1: mixing Co, CoO and LiH according to the mass ratio of 5:2:2, and then placing the mixture into a ball mill for grinding under the protection of argon, wherein the rotating speed of the ball mill is 400r/min, and the ball milling is carried out for 12 hours; the pressure intensity is 3 MPa; the temperature is 80 ℃; after ball milling, the metal powder was sieved through an 80 μm sieve and ball milling was continued until the metal powder passed.
Step 2: Co/CoO/LiH composite and NH4BF4Mixing according to the mass ratio of 100:1, grinding for 1 hour, heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 3 hours to obtain the composite material with the metal-fluorine-based net-shaped porous structure on the surface.
And step 3: and (3) putting the composite material prepared in the step (2), polyvinyl alcohol and polyacrylic acid into a high-pressure reaction kettle according to the mass ratio of 4:1:1, adding sufficient water and ethanol, stirring at a high speed, heating to 160 ℃, reacting for 24 hours to obtain a Co/CoO/LiH coordination polyacrylic acid precursor, washing with deionized water, and drying in an oven at 80 ℃.
And 4, step 4: and (3) putting the Co/CoO/LiH coordination polyacrylic acid precursor into a tubular furnace, introducing argon, heating to 600 ℃, and reacting for 4 hours to obtain the negative active material for the low-temperature lithium battery.
The multiplying power charge-discharge performance is shown in table 1, and the low-temperature charge-discharge performance is shown in table 2.
TABLE 1 Rate Charge and discharge Properties
Figure DEST_PATH_IMAGE001
TABLE 2 Low temperature Charge/discharge Properties
Figure 414907DEST_PATH_IMAGE002
Example 2
Step 1: mixing Ni, NiO and LiH according to the mass ratio of 5:2:2, and then placing the mixture into a ball mill for milling for 10 hours under the protection of argon, wherein the rotating speed of the ball mill is 400 r/min; the pressure intensity is 3 MPa; the temperature is 80 ℃; after ball milling, the metal powder was sieved through an 80 μm sieve and ball milling was continued until the metal powder passed.
Step 2: Ni/NiO/LiH composite and NH4And F, mixing according to the mass ratio of 100:2, grinding for 1 hour, heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 3 hours to obtain the composite material with the metal-fluorine-based net-shaped porous structure on the surface.
And step 3: and (3) putting the composite material prepared in the step (2), polyvinyl alcohol and aromatic acid into a high-pressure reaction kettle according to the mass ratio of 4:1:1, adding sufficient N, N-dimethylformamide and ethanol, stirring at a high speed, heating to 160 ℃, reacting for 24 hours to obtain a Ni/NiO/LiH coordination polyvinyl alcohol precursor, washing with deionized water, and drying in an oven at 80 ℃.
And 4, step 4: and putting the Ni/NiO/LiH coordinated polyvinyl alcohol precursor into a tubular furnace, introducing argon, heating to 600 ℃, and reacting for 4 hours to obtain the negative active material for the low-temperature lithium battery.
The multiplying power charge-discharge performance is shown in table 3, and the low-temperature charge-discharge performance is shown in table 4.
TABLE 3 multiplying power charge and discharge Properties
Figure DEST_PATH_IMAGE003
TABLE 4 Low temperature Charge/discharge Properties
Figure 744258DEST_PATH_IMAGE004
Example 3
Step 1: mixing Cu, CuO and LiH according to the mass ratio of 5:3:2, and then placing the mixture into a ball mill for grinding under the protection of argon, wherein the rotating speed of the ball mill is 400r/min, and the ball milling is carried out for 10 hours; the pressure intensity is 3 MPa; the temperature is 80 ℃; after ball milling, the metal powder was sieved through an 80 μm sieve and ball milling was continued until the metal powder passed.
Step 2: Cu/CuO/LiH composite material and NH4PF6Mixing according to the mass ratio of 100:0.5, grinding for 1 hour, heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 3 hours to obtain the composite material with the metal-fluorine-based net-shaped porous structure on the surface.
And step 3: and (3) putting the composite material prepared in the step (2), polyvinyl alcohol and polyacrylic acid into a high-pressure reaction kettle according to the mass ratio of 4:1:1, adding sufficient N, N-dimethylformamide and methanol, stirring at a high speed, heating to 160 ℃, reacting for 24 hours to obtain a Cu/CuO/LiH coordination polyvinyl alcohol precursor, washing with deionized water, and drying in an oven at 80 ℃.
And 4, step 4: and putting the Cu/CuO/LiH coordinated polyvinyl alcohol precursor into a tubular furnace, introducing argon, heating to 600 ℃, and reacting for 4 hours to obtain the negative active material for the low-temperature lithium battery.
The multiplying power charge-discharge performance is shown in Table 5, and the low-temperature charge-discharge performance is shown in Table 6.
TABLE 5 multiplying power charge and discharge Properties
Figure DEST_PATH_IMAGE005
TABLE 6 Low temperature Charge/discharge Properties
Figure 5475DEST_PATH_IMAGE006
Example 4
Step 1: adding Mn and MnO2Mixing LiH according to the mass ratio of 5:3:2, and then placing the mixture into a ball mill for grinding under the protection of argon, wherein the rotating speed of the ball mill is 400r/min, and the ball milling is carried out for 10 hours; the pressure intensity is 3 MPa; the temperature is 80 ℃; after ball milling, the metal powder was sieved through an 80 μm sieve and ball milling was continued until the metal powder passed.
Step 2: Mn/MnO2LiH composite material and NH4PF6Mixing according to the mass ratio of 100:0.5, grinding for 1 hour, heating to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 3 hours to obtain the metal-fluorine-based net-shaped material with the surfaceA composite material of porous structure.
And step 3: putting the composite material prepared in the step 2, polyethylene glycol and polyacrylic acid into a high-pressure reaction kettle according to the mass ratio of 4:1:1, adding sufficient N, N-dimethylacetamide and ethanol, stirring at a high speed, heating to 160 ℃, and reacting for 24 hours to obtain Mn/MnO2And the/LiH coordinated polyvinyl alcohol precursor is washed by deionized water and then is dried in an oven at 80 ℃.
And 4, step 4: Mn/MnO2Putting the LiH coordination polyvinyl alcohol precursor into a tubular furnace, introducing argon, heating to 600 ℃, and reacting for 4 hours to obtain the negative active material for the low-temperature lithium battery.
The multiplying power charge-discharge performance is shown in Table 7, and the low-temperature charge-discharge performance is shown in Table 8.
TABLE 7 multiplying power charge and discharge performance
Figure DEST_PATH_IMAGE007
TABLE 8 Low temperature Charge/discharge Properties
Figure 739600DEST_PATH_IMAGE008
Comparative example
Step 1: adding 50 parts of petroleum coke, 20 parts of needle coke, 20 parts of intermediate phase carbon microspheres and 30 parts of isotropic coke into a ball mill for crushing to obtain mixed powder.
Step 2: ultrasonically stirring the mixed powder and excessive perchloric acid for 2 hours, separating the powder by using a centrifugal machine, washing the powder by using purified water and ethanol respectively until the pH value is 8-9, drying the powder for 24 hours at 60 ℃, keeping the temperature for 2 hours at 800 ℃ under the protection of inert gas, and finally cooling to room temperature to obtain the expanded graphite.
And step 3: 10 parts by weight of expanded graphite, 1 part by weight of coal tar and 50 parts by weight of tetrahydrofuran are mixed and stirred at high speed for 1 hour.
And 4, step 4: and putting the agglomerated granules coated with the carbon source in an inert protective atmosphere at 1500 ℃ for carbonization and sintering treatment for 10 hours.
And 5: and placing the powder after the carbonization sintering treatment in an inert protective atmosphere, and performing graphitization sintering treatment for 48h at 3000 ℃.
Step 6: and mixing 100 parts by weight of the powder after the graphitization sintering treatment with 10 parts by weight of amorphous carbon, and stirring at a high speed for 1h to obtain the low-temperature lithium battery negative electrode material.
The negative electrode materials prepared in example 1 and comparative example were compared with batteries made of the same positive electrode, separator and electrolyte, and the capacity and charge/discharge performance were measured, and the results are shown in table 9. And (3) testing conditions are as follows: 25 +/-2 ℃ and relative humidity of 50-75%.
TABLE 9 comparison of initial specific capacity and Charge/discharge Properties
Figure DEST_PATH_IMAGE009
As can be seen from table 9, the lithium ion battery using the metal and the oxide thereof as the negative active material has higher specific capacity, cycle capacity retention rate, and better low-temperature performance.

Claims (6)

1. A preparation method of a negative active material for a low-temperature lithium battery is characterized in that the preparation process comprises the following steps:
(1) mixing metal and its oxide with lithium hydride according to the mass ratio of (2-8) to (1-4) to (0.1-3);
(2) ball-milling the mixed powder in an inert gas atmosphere to obtain a metal and an oxide/lithium hydride composite material thereof; the ball milling rotation speed is 300-500 r/min, the ball milling time is 1-30 hours, the pressure is 1-10 MPa, the temperature is 60-80 ℃, and the particle size of the metal and oxide powder thereof after ball milling is 1-100 mu m;
(3) uniformly mixing metal and oxide thereof/lithium hydride composite material with a fluorine-containing compound according to the mass ratio of 100 (0.5-5), and grinding after mixing;
(4) carrying out heat treatment on the material ground in the step (3) at the temperature of 200-800 ℃ for 1-5 hours to obtain a composite material with a metal-fluorine-based net-shaped porous structure on the surface;
(5) putting the composite material with the metal-fluorine-based net-shaped porous structure on the surface, the hydroxyl organic polymer and the carboxylic acid in the mass ratio of (1-5): 1:1 into a high-pressure reaction kettle, adding a polar solvent into the reaction kettle, violently stirring and dissolving, heating to 100-200 ℃, reacting for 1-60 hours to obtain a metal and an oxide/lithium hydride coordination polymer precursor thereof, washing and drying the product for later use; the hydroxyl organic polymer is one of polyvinyl alcohol, polyethylene glycol and hydroxyl-terminated polybutadiene; the carboxylic acid is one of polyacrylic acid and aromatic acid;
(6) and putting the metal and the oxide thereof/lithium hydride coordination polymer precursor into a tubular furnace with inert gas, heating to 200-800 ℃, and reacting for 1-10 hours to obtain the negative active material for the low-temperature lithium battery.
2. The method of claim 1, wherein the metal and the oxide thereof is one of magnesium and an oxide thereof, cobalt and an oxide thereof, aluminum and an oxide thereof, germanium and an oxide thereof, tin and an oxide thereof, lead and an oxide thereof, antimony and an oxide thereof, gallium and an oxide thereof, cadmium and an oxide thereof, silver and an oxide thereof, manganese and an oxide thereof, molybdenum and an oxide thereof, vanadium and an oxide thereof.
3. The method of claim 1, wherein the fluorine-containing compound is NH4F、NH4PF6、（NH4）3AlF6、NH4BF4One or more of them.
4. The method of claim 1, wherein the inert gas is argon.
5. The method of claim 1, wherein the polar solvent is one or more of water, methanol, ethanol, N-dimethylformamide, and N, N-dimethylacetamide.
6. A negative active material for a low temperature lithium battery prepared by the method of any one of claims 1 to 5.
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Address after: 257000 north of Gangcheng road and west of Gangxi Second Road, dongyinggang Economic Development Zone, Dongying City, Shandong Province

Patentee after: Shandong Yiwei New Material Co.,Ltd.

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Patentee before: CHENDU NEW KELI CHEMICAL SCIENCE Co.,Ltd. CHINA