CN110190327B - Lithium ion battery and preparation method thereof - Google Patents

Lithium ion battery and preparation method thereof Download PDF

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Publication number
CN110190327B
CN110190327B CN201910463238.0A CN201910463238A CN110190327B CN 110190327 B CN110190327 B CN 110190327B CN 201910463238 A CN201910463238 A CN 201910463238A CN 110190327 B CN110190327 B CN 110190327B
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bauxite
positive
lithium ion
ion battery
positive electrode
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CN110190327A (en
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贺思如
杨金林
王仲明
吴吉强
其他发明人请求不公开姓名
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Hunan Dianjiangjun New Energy Co ltd
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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Abstract

The invention relates to a lithium ion battery, which comprises a positive pole piece, a negative pole piece, a diaphragm, a shell and electrolyte, wherein the positive pole piece comprises a positive current collector and a positive active layer coated on the surface of the positive current collector, the positive active layer comprises a positive composite material, a conductive agent and a binder A in a mass ratio of 90-99: 0.5-5, the positive composite material comprises a positive material and a secondary clay or secondary bauxite coating layer coating the positive material, and the diaphragm is a composite diaphragm comprising a diaphragm matrix and a bauxite layer. The lithium ion battery provided by the invention is rich in mineral ions such as aluminum, silicon, magnesium and the like, can effectively improve the rate capability, the cycle performance, the low-temperature performance and the safety performance of the battery, improve the electronic/ionic conductivity of a battery material, improve the heat resistance and the liquid absorption rate of a diaphragm, improve the interface combination between the diaphragm and a positive plate and a negative plate, and reduce the interface resistance between electrolyte and an electrode material.

Description

Lithium ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery and a preparation method thereof.
Background
The lithium ion battery has the advantages of high specific energy, high working voltage, long cycle life, low self-discharge rate, no memory effect and the like, and is widely applied to the field of electronic equipment. With the continuous improvement of technology, lithium ion batteries are being applied to more fields, such as aerospace, automobiles, field devices, and the like. Meanwhile, higher use requirements are provided for the lithium ion battery, and higher energy density, rate capability, cycle performance and the like are required. Researchers are also continuously developing new materials or further modifying existing materials by compounding, doping, coating and the like. Such as the patent "LiAlO2The preparation method of the spinel-coated lithium manganate cathode material (patent application number: 201210379357.6) comprises the following steps: a. taking electrolytic manganese dioxide, lithium carbonate and chromium sesquioxide as raw materials, and batching, crushing and mixing; b. placing the mixed raw materials into an air atmosphere sintering furnace for sintering, crushing, sieving and mixing for the second time; c. placing the secondarily mixed material in an air atmosphere sintering furnace for heat preservation; d. crushing and mixing the obtained secondary sintered product and lithium fluoride; e. d, placing the mixture obtained in the step d in an air atmosphere sintering furnace; f. and preparing a mixed aqueous solution of lithium hydroxide monohydrate and aluminum isopropoxide for coating. In the patent, electrolytic manganese dioxide, lithium carbonate and chromium sesquioxide are sintered and sieved for multiple times, then are mixed and sintered with lithium fluoride, and finally are coated with liquid, so that the method has the advantages of multiple used raw materials, complex preparation process, high cost and no contribution to realizing industrial application.
Disclosure of Invention
The invention aims to solve the technical problem of how to prepare a lithium ion battery which has simple preparation process, low cost and good battery performance such as rate performance, cycle performance, low-temperature performance and safety performance and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a lithium ion battery comprises a positive pole piece, a diaphragm, a negative pole piece, a shell and electrolyte, wherein the positive pole piece, the diaphragm and the negative pole piece are packaged in the shell after being wound or laminated in the above sequence, and the electrolyte is injected into the shell;
the positive pole piece comprises a positive pole current collector and a positive pole active layer coated on the surface of the positive pole current collector, wherein the positive pole active layer comprises a positive pole composite material, a conductive agent and a binder A in a mass ratio of 90-99: 0.5-5, the positive pole composite material comprises a positive pole material and a secondary clay or secondary bauxite coating layer coating the positive pole material, and the mass fraction of the secondary clay or secondary bauxite coating layer in the positive pole composite material is 0.5-10%; and is
The membrane is a composite membrane comprising a membrane substrate and a bauxite layer, wherein the bauxite layer contains 70-99 mass% of bauxite nano particles and 1-30 mass% of a binder B and is coated on the surface of the membrane substrate.
Preferably, the positive electrode material is selected from one or more of lithium manganate, lithium iron phosphate, a lithium-rich manganese-based positive electrode material, a lithium cobaltate positive electrode material, a nickel-cobalt-manganese and nickel-cobalt-aluminum ternary positive electrode material.
Preferably, the conductive agent is selected from one or more of carbon black, carbon nanotubes, acetylene black, graphene and carbon nanofibers.
Preferably, the binder A is selected from one or more of a mixture of sodium carboxymethylcellulose and styrene butadiene rubber, polyvinylidene fluoride and polyacrylic acid.
Preferably, the binder B is one or more selected from polyvinylidene fluoride, polyvinyl alcohol, polyvinyl acetate and styrene-butadiene latex.
The invention also discloses a preparation method of the lithium ion battery, which comprises the following steps:
removing magnetic substances in the primary clay or bauxite to obtain secondary clay or secondary bauxite;
mixing the secondary clay or the secondary bauxite with a positive electrode material according to a mass ratio of 0.5-10: 90-100, and grinding to obtain a mixture;
sintering the mixture at 600-1000 ℃ to obtain a positive electrode composite material;
mixing a conductive agent, a binder A, the positive electrode composite material and a solvent to prepare positive electrode active slurry;
coating the positive active slurry on the surface of a positive current collector to prepare a positive pole piece;
dispersing the binder B in a dispersant to form a uniform binder dispersion liquid;
adding bauxite nano particles into the adhesive dispersion liquid, and forming uniform bauxite slurry after homogenization treatment;
coating the bauxite slurry on the surface of a membrane substrate and solidifying to obtain a composite membrane;
and assembling the positive pole piece, the composite diaphragm, the negative pole piece and the electrolyte into the lithium ion battery.
Specifically, the bauxite nanoparticles are prepared by the following method: the bauxite is subjected to heat treatment at 300-800 ℃, and then ground.
Preferably, the bauxite is heated to 300-800 ℃ at the speed of 3-8 ℃/min, then the temperature is kept for 30-180 min, and grinding is carried out for 30-120 min after cooling, so as to obtain the bauxite nanoparticles.
Preferably, the step of sintering the mixture at 600-1000 ℃ to obtain the positive electrode composite material comprises: and (3) after the mixture reaches the specified temperature of 600-1000 ℃ at the heating rate of 5-10 ℃/min, carrying out heat preservation sintering for 6-20 hours.
Preferably, the step of removing the magnetic substances from the primary clay or bauxite to obtain the secondary clay or bauxite is performed by placing the primary clay or bauxite into a pipeline iron remover.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the positive pole piece is prepared by using native clay or bauxite as a raw material, and the diaphragm is prepared by using bauxite, wherein the native clay or bauxite is wide in source, rich in resource, low in price and environment-friendly.
the lithium ion battery prepared by the invention is rich in aluminum, contains mineral ions such as silicon and magnesium, can effectively improve the rate capability, the cycle performance, the low-temperature performance and the safety performance of the battery, improves the electronic/ionic conductivity of a battery material, improves the heat resistance and the liquid absorption rate of a diaphragm, improves the interface combination between the diaphragm and the positive and negative plates, and reduces the interface resistance between electrolyte and an electrode material.
the preparation method has simple steps and low cost, and is easy to realize industrial application.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a graph comparing the rate performance of a lithium ion battery of example 1 with that of a conventional battery of comparative example 1;
FIG. 2 is a graph showing the comparison of cycle discharge at 35C for the lithium ion battery of example 1 and the conventional battery of comparative example 1;
FIG. 3 is a graph showing the change of voltage and temperature with time during the needling process of the lithium ion battery in example 1;
FIG. 4 is a graph showing the change of voltage and temperature with time during the needling process of the conventional battery in comparative example 1;
FIG. 5 is the 0.2C discharge curve at-40 ℃ for the lithium ion battery of example 1;
FIG. 6 is a 0.2C discharge curve at-40 ℃ for a conventional battery in comparative example 1;
FIG. 7 is a graph of capacity retention after 200 cycles at 35C for lithium ion batteries made with different ratios of secondary clay to lithium manganate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The invention discloses a preparation method of a lithium ion battery, which comprises the following steps:
the primary clay or bauxite is put into a pipeline iron remover, and the magnetic substances in the primary clay or bauxite are removed to obtain secondary clay or secondary bauxite;
mixing secondary clay or secondary bauxite and a positive electrode material according to a mass ratio of 0.5-10: 90-100, and grinding to obtain a mixture; the positive electrode material is selected from one or more of lithium manganate, lithium iron phosphate, a lithium-rich manganese-based positive electrode material, a lithium cobaltate positive electrode material, nickel-cobalt-manganese and nickel-cobalt-aluminum ternary positive electrode material;
sintering the mixture at 600-1000 ℃ to obtain the anode composite material, wherein the sintering temperature rise rate is 5-10 ℃/min, the heat preservation temperature range is 600-1000 ℃, and the sintering time is 6-20 h;
mixing a conductive agent, a binder A, a positive electrode composite material and a solvent to prepare positive electrode active slurry; the conductive agent is one or more of carbon black, carbon nano tubes, acetylene black, graphene and carbon nano fibers; the binder A is one or more of a mixture of sodium carboxymethylcellulose and styrene butadiene rubber, polyvinylidene fluoride and polyacrylic acid, and the mass ratio of the sodium carboxymethylcellulose to the styrene butadiene rubber is 1: 1;
coating the positive active slurry on the surface of a positive current collector to prepare a positive pole piece;
dispersing the binder B in a dispersant to form a uniform binder dispersion liquid; the binder B is one or more of polyvinylidene fluoride, polyvinyl alcohol, polyvinyl acetate and styrene-butadiene latex; the dispersant is one or more of glycerol, isopropanol, N-methyl pyrrolidone, sodium dodecyl benzene sulfonate, octyl phenol polyoxyethylene and deionized water;
heating bauxite to 300-800 ℃ at the speed of 3-8 ℃/min, then preserving heat for 30-180 min, cooling, and grinding for 30-120 min to obtain bauxite nanoparticles; the grinding adopts ball milling, sand milling or three-dimensional mixing; adding the bauxite nano particles into the adhesive dispersion liquid, and forming uniform bauxite slurry after homogenizing treatment;
coating bauxite slurry on the surface of a membrane substrate and solidifying to obtain a composite membrane; the diaphragm substrate is one of a PE diaphragm, a PP/PE composite diaphragm, a PP/PE/PP composite diaphragm, a PET diaphragm, a PI diaphragm, a PA diaphragm, a polyvinylidene fluoride diaphragm, a glass fiber diaphragm, a cellulose composite diaphragm, a polyester diaphragm, a polyimide diaphragm and a polyamide diaphragm;
and finally assembling the positive pole piece, the composite diaphragm, the negative pole piece and the electrolyte into the lithium ion battery.
Examples
Example 1
The preparation method of the lithium ion battery provided by the specific embodiment includes the following steps:
carrying out magnetic separation treatment on the primary clay: placing the primary clay in a pipeline iron remover to remove Fe and Fe2O3And NiO and the like, and the treatment time is 0.5h to obtain the secondary clay. The positive electrode material is lithium manganate, 1.6g of secondary clay and 45g of lithium manganate are mixed and are subjected to ball milling in a SPEX 8000 ball mill for 12 hours to obtain a mixture, wherein the mass ratio of the secondary clay to the lithium manganate is 3.5: 100. And (3) placing the mixture into a tube furnace for air sintering, wherein the sintering time is 8 h. The sintering temperature control comprises a temperature rise process and a constant temperature process, wherein the temperature rise rate of the temperature rise process is 5 ℃/min, and the temperature of the constant temperature process is controlled to be 800 ℃. And after sintering is finished, cooling to obtain the anode composite material, wherein the mass fraction of the secondary clay is 3.4%.
The conductive agent adopts carbon black, the binder A adopts polyvinylidene fluoride, and the mass ratio of the positive electrode composite material to the carbon black to the polyvinylidene fluoride is 96: 2:2, adding N-methyl pyrrolidone, and uniformly mixing to obtain the positive active slurry, wherein the viscosity of the positive active slurry is controlled to 10000Pa.s, and the solid content is controlled to 60%. And coating the positive active slurry on two sides of the aluminum foil, drying in an oven at 80 ℃ for 12 hours, and slitting to obtain the positive pole piece.
2g of bauxite ore is put into a muffle furnaceHeating to 350 ℃ at the speed of 3 ℃/min, then preserving heat for 30min, cooling and then ball-milling for 10min to obtain the bauxite nano-scale particles. The binder B is styrene-butadiene latex, the dispersing agent is deionized water, and 0.5g of styrene-butadiene latex is dispersed in 10mL of deionized water. Adding the bauxite nano-scale particles into the binder B dispersion liquid, magnetically stirring for 1h, performing ultrasonic treatment for 30min, and adjusting the viscosity of the slurry to 600mPa & s by using the amount of deionized water. Then stirring for 1h by magnetic force, and carrying out ultrasonic treatment for 30min to obtain uniform bauxite slurry. The bauxite slurry is uniformly coated on the surface of the PP and PE composite diaphragm at room temperature, and the coating thickness is 5 mu m. Placing in a 30 deg.C thermostat for 6h, and then in a 60 deg.C vacuum environment for 6h to obtain a membrane with average bauxite layer loading of 1.6mg cm-2。
Winding the positive pole piece, the diaphragm and the negative pole piece in the sequence to assemble a half-cell, putting the half-cell into a shell, performing side sealing, and injecting electrolyte, wherein the electrolyte comprises LiPF6EC/PC with a molar ratio of 1:1, LiPF6The molar concentration of (b) is l.08mol/L. And then, carrying out top sealing to prepare a full cell, and carrying out formation, air extraction, volume division and chemical performance testing.
Comparative example 1
The positive electrode material adopts lithium manganate, the diaphragm adopts a PP and PE composite diaphragm, and the unmodified common lithium ion battery is prepared according to the preparation method and the steps of the pole piece and the battery in the embodiment 1.
Fig. 1 is a graph showing discharge contrast curves at 1C, 10C, 20C, and 35C for the lithium ion battery of example 1 and the unmodified general battery of comparative example 1, respectively. As can be seen from fig. 1, the discharge voltage plateau of the lithium ion battery prepared in example 1 is higher and smoother at both high and low rates than that of the ordinary battery in comparative example 1 without modification, and the discharge capacity is slightly higher than that of the ordinary battery without modification.
Fig. 2 is a graph comparing the cycle discharge at 35C for the lithium ion battery of example 1 and the unmodified conventional battery of comparative example 1. As can be seen from fig. 2, the capacity of the lithium ion battery in example 1 decays slowly and steadily, and the capacity can still be maintained at 89% or more after 200 cycles at 35C, while the unmodified ordinary battery in comparative example 1 has disordered data at 35C, fast capacity decay, and performance inferior to that of the lithium ion battery in example 1, which shows that the rate performance of the battery can be effectively improved by modifying the surface of the material with natural minerals.
Fig. 3 and 4 are graphs showing the change of voltage and temperature with time during the needling process of the lithium ion battery in example 1 and the unmodified general battery in comparative example 1, respectively. As can be seen from fig. 3 and 4, in the lithium ion battery in example 1, the voltage is stable during the needling process, the original voltage is maintained at about 4.0V, the temperature is still normal temperature 10 seconds after the needling, and even if the temperature is 37 ℃ after the needling for 70 seconds. In contrast, in the comparative example 1, the voltage is unstable in the needling process of the common battery, the voltage drops to 0V after 17 seconds of needling, the temperature also rises steeply, the temperature reaches 110 ℃ after 20 seconds of needling, and a huge potential safety hazard exists, which indicates that the lithium ion battery in the example 1 is high in safety.
Fig. 5 and 6 are discharge curves of the lithium ion battery in example 1 and the common battery in comparative example 1 with the same capacity (3500mAh) under the same low temperature condition, respectively, and it can be seen from fig. 5 and 6 that the lithium ion battery in example 1 has higher discharge voltage and discharge capacity, the lithium ion battery can release 72% of initial capacity at low temperature of-40 ℃, while the common battery in comparative example 1 can only release 60% of initial capacity, which shows that the lithium ion battery of the present embodiment has better low temperature performance than the common battery, and the present solution has certain effect on improvement of low temperature performance of the lithium ion battery.
Example 2
Example 2 differs from example 1 in that the mass ratio of the secondary clay to lithium manganate was 0.5: 100.
Example 3
Example 3 is different from example 1 in that the mass ratio of the secondary clay to the lithium manganate is 5: 100.
Example 4
Example 4 differs from example 1 in that the mass ratio of the secondary clay to lithium manganate was 7: 100.
Example 5
Example 5 differs from example 1 in that the mass ratio of the secondary clay to lithium manganate was 10: 100.
Comparative example 2
Comparative example 2 differs from example 1 in that the mass ratio of secondary clay to lithium manganate was about 0.1: 100.
Comparative example 3
Comparative example 3 differs from example 1 in that the mass ratio of secondary clay to lithium manganate was about 20: 100.
Example 6
Example 6 differs from example 1 in that the raw clay in example 1 was replaced with bauxite.
Comparative example 4
Comparative example 4 differs from example 6 in that the bauxite in example 7 was replaced with Al2O3。
Example 7
The preparation method of the lithium ion battery provided by the specific embodiment includes the following steps:
carrying out magnetic separation treatment on the primary clay: placing the primary clay in a pipeline iron remover to remove Fe and Fe2O3And NiO and the like, and the treatment time is 0.5h to obtain the secondary clay. The positive electrode material is a nickel-cobalt-manganese ternary positive electrode material, secondary clay with the mass ratio of 3.5:100 and the nickel-cobalt-manganese ternary positive electrode material are mixed and subjected to sanding treatment, and the sanding time is 6 hours. The mixture was placed in a tube furnace and sintered in air for 6 h. The sintering temperature control comprises a temperature rise process and a constant temperature process, wherein the temperature rise rate of the temperature rise process is 5 ℃/min, and the temperature of the constant temperature process is controlled to be 600 ℃. And after sintering is finished, cooling to obtain the anode composite material, wherein the mass fraction of the secondary clay is 3.4%.
The conductive agent adopts a carbon nano tube, and the adhesive A adopts a mixture of 1:1, the mass ratio of the positive electrode composite material to the mixture of the carbon nano tube, the sodium carboxymethyl cellulose and the styrene butadiene rubber is 97:1.5:1.5, deionized water is added and uniformly mixed to prepare positive electrode active slurry, the viscosity of the positive electrode active slurry is controlled to be 8000Pa.s, and the solid content is controlled to be 55%. And coating the positive active slurry on two sides of the aluminum foil, drying in an oven at 80 ℃ for 12 hours, and slitting to obtain the positive pole piece.
Putting 2g of bauxite into a muffle furnace, heating to 300 ℃ at the speed of 3 ℃/min, then preserving heat for 30min, cooling and then ball-milling for 10min to obtain the bauxite nano-scale particles. The binder B is polyvinylidene fluoride, the dispersing agent is N-methyl pyrrolidone, and 0.5g of polyvinylidene fluoride is dispersed in 10mL of N-methyl pyrrolidone. Adding the bauxite nano-scale particles into the binder B dispersion liquid, magnetically stirring for 1h, performing ultrasonic treatment for 30min, and adjusting the viscosity of the slurry to 600mPa & s by adjusting N-methyl pyrrolidone. Then stirring for 1h by magnetic force, and carrying out ultrasonic treatment for 30min to obtain uniform bauxite slurry. The bauxite slurry was uniformly coated on the PE membrane at room temperature to a coating thickness of 5 μm. Placing the membrane in a 30 ℃ constant temperature oven for 6h, and then placing the membrane in a 60 ℃ vacuum environment for 6h to obtain the membrane, wherein the average loading capacity of a bauxite layer is 1.52 mg-cm-2。
Winding the positive pole piece, the diaphragm and the negative pole piece in the sequence to assemble a half-cell, putting the half-cell into a shell, performing side sealing, and injecting electrolyte, wherein the electrolyte comprises LiPF6EC/PC with a molar ratio of 1:1, LiPF6The molar concentration of (b) is l.08mol/L. And then, carrying out top sealing to prepare a full cell, and carrying out formation, air extraction, volume division and chemical performance testing.
Example 8
The preparation method of the lithium ion battery provided by the specific embodiment includes the following steps:
carrying out magnetic separation treatment on the primary clay: placing the primary clay in a pipeline iron remover to remove Fe and Fe2O3And NiO and the like, and the treatment time is 3 hours to obtain secondary clay. The positive electrode material is lithium cobaltate, secondary clay with the mass ratio of 10:100 is mixed with the lithium cobaltate, and sanding treatment is carried out, wherein the sanding time is 20 hours. The mixture was placed in a tube furnace and sintered in air for 20 h. The sintering temperature control comprises a temperature rise process and a constant temperature process, wherein the temperature rise rate of the temperature rise process is 10 ℃/min, and the temperature of the constant temperature process is controlled to be 1000 ℃. And after sintering is finished, cooling to obtain the anode composite material, wherein the mass fraction of the secondary clay is 9%.
The conductive agent adopts acetylene black, and the adhesive A adopts a mixture of acetylene black and binder A in a mass ratio of 1:1, the mass ratio of the mixture of the sodium carboxymethylcellulose and the styrene butadiene rubber to the mixture of the positive electrode composite material, the acetylene black, the sodium carboxymethylcellulose and the styrene butadiene rubber is 90: 5:5, adding deionized water, and uniformly mixing to obtain the positive active slurry, wherein the viscosity of the positive active slurry is controlled to be 15000Pa.s, and the solid content is 65%. And coating the positive active slurry on two sides of the aluminum foil, drying in an oven at 80 ℃ for 12 hours, and slitting to obtain the positive pole piece.
Placing 2g of bauxite into a muffle furnace, heating to 800 ℃ at the speed of 3 ℃/min, then preserving heat for 30min, cooling and then ball-milling for 10min to obtain the bauxite nano-scale particles. The adhesive B is polyvinyl alcohol, and the dispersing agent is sodium dodecyl benzene sulfonate solution, wherein the mass ratio of the sodium dodecyl benzene sulfonate to the deionized water is 1:10, 0.5g of polyvinyl alcohol was dispersed in 10mL of a sodium dodecylbenzenesulfonate solution. Adding the bauxite nano-scale particles into the binder B dispersion liquid, magnetically stirring for 1h, performing ultrasonic treatment for 30min, and adjusting the viscosity of the slurry to 600mPa & s by adjusting the amount of the sodium dodecyl benzene sulfonate solution. Then stirring for 1h by magnetic force, and carrying out ultrasonic treatment for 30min to obtain uniform bauxite slurry. The bauxite slurry is uniformly coated on the surface of the pp membrane at room temperature, and the coating thickness is 5 mu m. Placing in a 50 deg.C constant temperature oven for 8 hr, and then placing in 80 deg.C vacuum environment for 16 hr to obtain a membrane with average bauxite layer loading of 1.62mg cm-2。
Winding the positive pole piece, the diaphragm and the negative pole piece in the sequence to assemble a half-cell, putting the half-cell into a shell, performing side sealing, and injecting electrolyte, wherein the electrolyte comprises LiPF6EC/PC with a molar ratio of 1:1, LiPF6The molar concentration of (b) is l.08mol/L. And then, carrying out top sealing to prepare a full cell, and carrying out formation, air extraction, volume division and chemical performance testing.
Example 9
The preparation method of the lithium ion battery provided by the specific embodiment includes the following steps:
carrying out magnetic separation treatment on the primary clay: placing the primary clay in a pipeline iron remover to remove Fe and Fe2O3、NAnd treating the magnetic substances such as iO for 2 hours to obtain secondary clay. The positive electrode material is selected from lithium manganate, secondary clay with the mass ratio of 5:100 is mixed with the lithium manganate and subjected to three-dimensional mixing, and the treatment time is 20 hours. The mixture was placed in a tube furnace and sintered in air for 15 h. The sintering temperature control comprises a temperature rise process and a constant temperature process, wherein the temperature rise rate of the temperature rise process is 7 ℃/min, and the temperature of the constant temperature process is controlled to be 800 ℃. And after sintering is finished, cooling to obtain the anode composite material, wherein the mass fraction of the secondary clay is 5%.
The conductive agent is a mixture of graphene and carbon nanofibers in a mass ratio of 1:1, and the binder A is a mixture of graphene and carbon nanofibers in a mass ratio of 1:1, the mass ratio of the positive electrode composite material, the mixture of graphene and carbon nanofibers and the mixture of carboxymethyl cellulose uranium and styrene butadiene rubber is 99:0.5:0.5, deionized water is added and uniformly mixed to prepare positive electrode active slurry, the viscosity of the positive electrode active slurry is controlled to be 10000Pa.s, and the solid content is 50%. And coating the positive active slurry on two sides of the aluminum foil, drying in an oven at 80 ℃ for 12 hours, and slitting to obtain the positive pole piece.
Putting 2g of bauxite into a muffle furnace, heating to 500 ℃ at the speed of 3 ℃/min, then preserving heat for 30min, cooling and then ball-milling for 10min to obtain the bauxite nano-scale particles. The adhesive B is polyvinyl acetate, the dispersing agent is a mixed solution of isopropanol and octylphenol polyoxyethylene with a molar ratio of 1:1, and 0.5g of polyvinyl acetate is dispersed in 10mL of a mixed solution of isopropanol and octylphenol polyoxyethylene. Adding the bauxite nano-scale particles into the adhesive B dispersion liquid, magnetically stirring for 1h, performing ultrasonic treatment for 30min, and adjusting the viscosity of the slurry to 600mPa & s by adjusting the amount of the mixed liquid of isopropanol and octylphenol polyoxyethylene. Then stirring for 1h by magnetic force, and carrying out ultrasonic treatment for 30min to obtain uniform bauxite slurry. And uniformly coating the bauxite slurry on the surface of the polyvinylidene fluoride diaphragm at room temperature, wherein the coating thickness is 5 mu m. Placing the membrane in a constant temperature oven at 50 deg.C for 7h, and then in a vacuum environment at 80 deg.C for 10h to obtain a membrane with average bauxite layer loading of 1.61mg cm-2。
The positive pole piece is connected with a positive electrode,The diaphragm and the negative pole piece are wound in the sequence and assembled into a half-cell, the half-cell is placed into a shell and subjected to side sealing, and electrolyte is injected, wherein the electrolyte comprises LiPF6EC/PC with a molar ratio of 1:1, LiPF6The molar concentration of (b) is l.08mol/L. And then, carrying out top sealing to prepare a full cell, and carrying out formation, air extraction, volume division and chemical performance testing.
The lithium ion batteries prepared in examples 1 to 9 and comparative examples 1 to 4 were subjected to a cycle discharge test, a needle prick test, and a low-temperature-40 ℃ discharge test, respectively, and the obtained test data are shown in table 1:
TABLE 1 comparison table of cyclic discharge test, acupuncture test, and low-temperature-40 deg.C discharge test data
Figure BDA0002078680270000111
Fig. 7 is a curve of capacity retention rates of different lithium ion batteries prepared by adjusting the ratio of secondary clay to lithium manganate after circulating for 200 times at 35C, when the ratio of secondary clay to lithium manganate is 1-10: 90-100, the capacity retention rate of the prepared lithium ion battery after circulating for 200 times at 35C is higher, and when the ratio of secondary clay to lithium manganate is 3.5:100, the capacity retention rate of the prepared lithium ion battery after circulating for 200 times at 35C is 89%, and the performance is optimal.
Comparative example 4 differs from example 6 in the replacement of bauxite with Al2O3As can be seen from table 1, the performance of the lithium ion battery prepared in comparative example 4 does not reach the performance of the lithium ion battery prepared in example 6. Because the bauxite has various components and reacts and interacts in the sintering process, the lithium ion battery prepared from the bauxite has excellent performance. The lithium ion battery prepared by the invention is rich in aluminum, also contains mineral ions such as silicon and magnesium, can effectively improve the conductivity of the battery material, improve the rate capability, the cycle performance, the safety performance and the low-temperature performance of the battery, improve the heat resistance and the liquid absorption rate of the diaphragm, and improve the interface combination between the diaphragm and the positive and negative plates.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (8)

1. A preparation method of a lithium ion battery is characterized by comprising the following steps:
removing magnetic substances in the bauxite to obtain the treated bauxite;
mixing the treated bauxite and a positive electrode material according to the mass ratio of 0.5-10: 90-100, and grinding to obtain a mixture;
sintering the mixture at 600-1000 ℃ to obtain a positive electrode composite material;
mixing a conductive agent, a binder A, the positive electrode composite material and a solvent to prepare positive electrode active slurry;
coating the positive active slurry on the surface of a positive current collector to prepare a positive pole piece;
dispersing the binder B in a dispersant to form a uniform binder dispersion liquid;
adding bauxite nano particles into the adhesive dispersion liquid, and forming uniform bauxite slurry after homogenization treatment;
coating the bauxite slurry on the surface of a membrane substrate and solidifying to obtain a composite membrane;
assembling the positive pole piece, the composite diaphragm, the negative pole piece and the electrolyte into a lithium ion battery,
the positive active slurry comprises the positive composite material, the conductive agent and the binder A in a mass ratio of 90-99: 0.5-5; in the positive composite material, the mass fraction of the bauxite coating layer after treatment is 0.5-10%; and is
The bauxite slurry contains 70-99 mass% of the bauxite nanoparticles and 1-30 mass% of the binder B;
the positive electrode material is selected from one or more of lithium manganate, lithium iron phosphate, a lithium-rich manganese-based positive electrode material, a lithium cobaltate positive electrode material or a nickel-cobalt-aluminum ternary positive electrode material.
2. The method for producing a lithium ion battery according to claim 1, characterized in that: the conductive agent is selected from one or more of carbon black, carbon nano-tube, graphene or carbon nano-fiber.
3. The method for producing a lithium ion battery according to claim 1 or 2, characterized in that: the binder A is selected from one or more of a mixture of sodium carboxymethylcellulose and styrene butadiene rubber, polyvinylidene fluoride or polyacrylic acid.
4. The method for producing a lithium ion battery according to claim 1 or 2, characterized in that: the binder B is selected from one or more of polyvinylidene fluoride, polyvinyl alcohol, polyvinyl acetate or styrene-butadiene latex.
5. The method for producing a lithium ion battery according to claim 1, characterized in that: the bauxite nano particles are prepared by the following method: the bauxite is subjected to heat treatment at 300-800 ℃, and then ground.
6. The method for producing a lithium ion battery according to claim 5, characterized in that: heating bauxite to 300-800 ℃ at the speed of 3-8 ℃/min, then preserving heat for 30-180 min, cooling, and grinding for 30-120 min to obtain bauxite nanoparticles.
7. The method for producing a lithium ion battery according to claim 1, characterized in that: the step of sintering the mixture at 600-1000 ℃ to obtain the positive electrode composite material comprises the following steps: and (3) after the mixture reaches the specified temperature of 600-1000 ℃ at the heating rate of 5-10 ℃/min, carrying out heat preservation sintering for 6-20 hours.
8. The method for producing a lithium ion battery according to claim 1, characterized in that: the step of removing magnetic substances from the bauxite to obtain the treated bauxite is performed by placing the bauxite in a pipeline de-ironing separator.
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