CN117317138B - Low-temperature lithium ion battery and preparation method thereof - Google Patents

Low-temperature lithium ion battery and preparation method thereof Download PDF

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CN117317138B
CN117317138B CN202311626243.1A CN202311626243A CN117317138B CN 117317138 B CN117317138 B CN 117317138B CN 202311626243 A CN202311626243 A CN 202311626243A CN 117317138 B CN117317138 B CN 117317138B
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coating
low
lithium ion
ion battery
mixture
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CN117317138A (en
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成天琼
奚睿
朱晓艳
李冰蕊
张雅荣
鲜建
陈溢卓
潘光彩
刘志昆
王金凤
龚文旭
李云
陈启章
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Sinocat Environmental Technology Co Ltd
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
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Abstract

The invention discloses a low-temperature lithium ion battery and a preparation method thereof, and relates to the technical field of low-temperature lithium ion batteries. The preparation method is used for preparing the low-temperature lithium ion battery. The invention optimizes and modifies the anode active material and the cathode coating of the traditional lithium iron phosphate battery, greatly promotes the deintercalation rate of lithium ions from the lithium iron phosphate anode material and the migration rate of lithium ions in the solid material at low temperature, and improves the low-temperature cycle performance and the rate capability of the lithium iron phosphate battery.

Description

Low-temperature lithium ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a low-temperature lithium ion battery and a preparation method thereof.
Background
The performance of lithium ion batteries at low temperatures is severely degraded, impeding their wide application in electric vehicles and smart grids. The main reason is that the reaction kinetics of the lithium ion battery at low temperature is lower, and the lithium ion battery is particularly characterized in that the migration rate of lithium ions in an electrode material at low temperature is sharply reduced, the SEI film resistance of a graphite negative electrode at low temperature is rapidly increased, the electrochemical polarization is remarkably increased, the diffusion rate of lithium ions in graphite is reduced, the intercalation of the graphite negative electrode is also limited, lithium dendrites are also formed in the repeated intercalation-deintercalation cycle process of the lithium ions, and the safety performance of the battery is greatly hidden trouble, so that the traditional graphite is not suitable for being used as an ideal negative electrode material of the low-temperature lithium ion battery. In order to solve the above problems, researchers have tried to introduce external or internal heating devices, or to construct solid-state batteries using solid electrolytes, or to use electrolyte additives and low-polarity solvents to improve intercalation kinetics, and to develop new electrode materials, but no suitable technology, structure and materials are currently used to improve, and there are still many effects on lithium ion migration rate, performance, etc. at low temperatures, which hinders popularization and application of lithium ion batteries.
Based on the above, the invention aims at improving the migration rate of lithium ions in a positive electrode solid material at low temperature and improving the dynamic performance of a traditional graphite negative electrode, thereby improving the low-temperature performance of a lithium ion battery.
Disclosure of Invention
The invention aims to provide a low-temperature lithium ion battery, which optimizes and modifies a positive electrode active material and a negative electrode coating of a traditional lithium iron phosphate battery, greatly promotes the deintercalation rate of lithium ions from the lithium iron phosphate positive electrode material and the migration rate of lithium ions from a solid material at low temperature, and improves the low-temperature cycle performance and the rate capability of the lithium iron phosphate battery. Meanwhile, the invention also provides a preparation method of the low-temperature lithium ion battery based on the low-temperature lithium ion battery.
The aim of the invention is mainly realized by the following technical scheme: the low-temperature lithium ion battery consists of a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive active material coating of the positive plate is lithium iron phosphate with a noble metal layer attached to the surface, the negative active material coating of the negative plate is a double coating, the middle-bottom coating of the double coating is graphite, and the surface coating is a transition metal chalcogenide.
Based on the technical scheme, the coating thickness ratio of the bottom coating to the surface coating of the negative electrode sheet is 5-20: 1, a step of; and the particle size of graphite is 5-30um, and the particle size of the transition metal chalcogenide is 35-80 um.
Based on the technical scheme, the noble metal element of the noble metal layer is any one or a mixture of more than two of platinum, palladium, rhodium, ruthenium, iridium and osmium, and the content of the noble metal accounts for 0.2-5% of the mass of the lithium iron phosphate.
Based on the technical proposal, the general formula of the transition metal chalcogenide is MX 2 C; wherein M is a transition metal element, and X is a chalcogen element.
Based on the technical scheme, the transition metal element is any one or a mixture of more than two of molybdenum, tungsten, niobium, titanium and rhenium, and the chalcogen element is any one or a mixture of more than two of sulfur, selenium and tellurium.
Meanwhile, the invention also provides a preparation method of the low-temperature lithium ion battery based on the low-temperature lithium ion battery, which comprises the following steps:
preparation of S1 cathode active Material
Adding lithium iron phosphate powder into a dispersing agent, and stirring for 0.5-2 h;
adding a noble metal salt solution into a dispersing agent containing lithium iron phosphate powder, and stirring for 1-3 hours;
adding a reducing agent, heating to 60-110 ℃, stirring for 1-6 hours, centrifuging, filtering, drying at 60-120 ℃ for 3-10 hours, and roasting at 200 ℃ for 5-8 hours to obtain optimized anode material powder;
preparation of S2 cathode active material coating
The optimized positive electrode material powder is taken, N-methyl pyrrolidone solvent, conductive carbon black and polyvinylidene fluoride are added, and uniformly mixed, and then the mixture is coated on an aluminum foil, and the positive electrode plate is obtained after drying, wherein the mass ratio of the positive electrode material powder to the conductive carbon black to the polyvinylidene fluoride is 86-97%, 2-7% and 1-7%, and the solid content of the coating slurry is 50-70%;
s3 preparation of primer coating
And adding solvent water, conductive carbon black, sodium carboxymethyl cellulose and styrene-butadiene rubber into the natural graphite powder, uniformly mixing, and coating the mixture on a copper foil, wherein the mass ratio of the graphite powder to the conductive carbon black to the sodium carboxymethyl cellulose to the styrene-butadiene rubber is 90-97%, 2-5%, 1.3-3% and 1.5-5%, and the solid content of the coating slurry is 45-70%.
S4 preparation of surface coating
Preparation of S41 surface coating material
Adding a precursor containing M and X and hexadecyl trimethyl ammonium bromide into a soluble solvent for dissolution and uniform mixing to form slurry, performing hydrothermal reaction, controlling the temperature of the hydrothermal reaction to be 200-250 ℃ and the reaction time to be 10-36 h, centrifugally filtering a product obtained after the reaction, repeatedly flushing the product with ethanol and water for multiple times, and drying to obtain a surface layer coating material;
s42 application of top coating
Adding solvent water, conductive carbon black, carbon nano tube, sodium carboxymethyl cellulose and acrylic acid into the prepared surface coating material, uniformly mixing, coating the mixture on the surface coating, and drying to obtain a negative plate, wherein the mass ratio of the surface coating material to the conductive carbon black to the carbon nano tube to the sodium carboxymethyl cellulose to the acrylic acid is 87.5-97%, 1.5-5%, 0.1-2%, 0.7-2.5% and 0.7-3%, and the solid content of the coating slurry is 45-70%;
s5 preparation of battery cell
And sequentially rolling, cutting, laminating, welding tabs, sealing, injecting liquid, forming and separating the prepared positive and negative plates to obtain the low-temperature lithium ion battery, wherein the electrolyte solvent in the liquid injection procedure is ethylene carbonate and dimethyl carbonate with the volume ratio of 1:1, and the electrolyte is lithium hexafluorophosphate with the molar concentration of 0.5-1.5 mol/L.
Based on the preparation method, in the step S1, the noble metal salt solution is any one or a mixture of more than two of nitrate solution, chlorate solution, hydroxylamine salt solution, oxalic acid amine salt solution and nitrosoamine salt solution.
Based on the preparation method, in the step S1, the dispersing agent is a hydrophobic solvent, the hydrophobic solvent is any one or a mixture of more than two of n-hexane, petroleum ether, n-pentane and n-heptane, and the adding volume amount of the dispersing agent is 5-100 times of the mass of the lithium iron phosphate.
Based on the preparation method, in the step S1, the reducing agent is formaldehyde, hydrazine hydrate or NaBH 4 Any one or a mixture of more than two of ethanol, glycol and glycerol, and the molar ratio of the addition amount of the reducing agent to the noble metal is 1-10: 1.
based on the preparation method, in the step S41, the precursor of M is any one or a mixture of more than two of ammonium molybdate, ammonium tungstate, ammonium niobate oxalate hydrate, ammonium rhenate and alkanolamine titanate; the precursor of X is any one or a mixture of more than two of thiourea, thioacetamide and selenourea; and the molar ratio of the precursor of M to the precursor of X is 1: 5-20.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the noble metal layer is formed by in-situ reduction on the surface of the lithium iron phosphate, and the noble metal has excellent catalytic effect, so that the reaction energy barrier can be reduced, and the deintercalation rate of lithium ions from the lithium iron phosphate anode material and the migration rate of lithium ions in the solid material are greatly promoted at low temperature; in addition, the transition metal chalcogenide compound prepared by the method has a two-dimensional layered structure, after being coated on the surface of a graphite carbon layer, the rapid ion channel of the chalcogenide compound and the excellent conductivity of a carbon material are combined, the formed structure has an expansion layer, the diffusion capacity of lithium ions can be further enhanced, and therefore better low-temperature cycle performance and rate capability are obtained.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention. In the drawings:
fig. 1 is a graph showing the low-temperature rate performance of the batteries prepared in examples 1 to 3 and comparative examples 1 to 3.
Detailed Description
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the description thereof is merely illustrative of the present invention and not intended to be limiting.
The first embodiment of the invention provides a low-temperature lithium ion battery which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein a positive active material coating of the positive plate is lithium iron phosphate with a noble metal layer attached to the surface, a negative active material coating of the negative plate is a double coating, a middle-bottom coating of the double coating is graphite, and a surface coating is a transition metal sulfur compound.
It should be noted that: compared with graphite, the transition metal sulfur compound has a two-dimensional layered structure, has good lithium ion insertion/extraction capability, can endow rapid charge and discharge performance along a specific direction, is a negative electrode material of a low-temperature lithium ion battery hopefully replacing graphite to be ideal, combines the two-dimensional transition metal sulfur compound with a graphite material, and forms a structure with an expansion layer, so that the diffusion capability of ions is further enhanced, better speed and circulation performance can be obtained, and meanwhile, the surface of the lithium iron phosphate positive electrode material is modified by using a noble metal active component, the noble metal has excellent catalytic effect, the reaction energy barrier can be reduced, and the migration rate of lithium ions in the positive electrode solid material at low temperature is enhanced, so that the low-temperature performance is improved.
Based on the above, the precious metal layer is formed on the surface of the lithium iron phosphate, the precious metal has excellent catalysis, the reaction energy barrier can be reduced, the deintercalation rate of lithium ions from the lithium iron phosphate anode material and the migration rate of lithium ions in the solid material are greatly promoted at low temperature, in addition, the transition metal chalcogenide prepared by the method has a two-dimensional layered structure, after being coated on the surface of the graphite carbon layer, the rapid ion channel of the chalcogenide and the excellent conductivity advantage of the carbon material are combined, the formed structure has an expansion layer, the diffusion capability of lithium ions can be further enhanced, so that better low-temperature cycle performance and rate performance are caused, meanwhile, the two-dimensional transition metal chalcogenide has better electrocatalysis, and abundant surface, subsurface and edge structures, the desolvation process of lithium ions at the interface of a graphite anode and an electrolyte is promoted, and the low-temperature cycle performance and rate performance of the lithium iron phosphate battery are remarkably improved through the simultaneous optimization of the anode material and the anode coating.
In specific implementation, the coating thickness ratio of the bottom coating to the surface coating of the negative electrode sheet is 5-20: 1, a step of; and the particle size of graphite is 5-30um, and the particle size of the transition metal chalcogenide is 35-80 um.
In specific implementation, the noble metal element of the noble metal layer is any one or a mixture of more than two of platinum, palladium, rhodium, ruthenium, iridium and osmium, and the content of the noble metal accounts for 0.2-5% of the mass of the lithium iron phosphate.
In particular embodiments, the transition metal chalcogenide has the formula MX 2 C; wherein M is a transition metal element, and X is a chalcogen element.
In the specific implementation, the transition metal element is any one or a mixture of more than two of molybdenum, tungsten, niobium, titanium and rhenium, and the chalcogen element is any one or a mixture of more than two of sulfur, selenium and tellurium.
The second embodiment of the invention provides a preparation method of a low-temperature lithium ion battery, which comprises the following steps:
preparation of S1 cathode active Material
Adding lithium iron phosphate powder into a dispersing agent, and stirring for 0.5-2 h;
adding a noble metal salt solution into a dispersing agent containing lithium iron phosphate powder, and stirring for 1-3 hours;
adding a reducing agent, heating to 60-110 ℃, stirring for 1-6 hours, centrifuging, filtering, drying at 60-120 ℃ for 3-10 hours, and roasting at 200 ℃ for 5-8 hours to obtain optimized anode material powder;
in the specific implementation, the noble metal salt solution is any one or a mixture of more than two of nitrate solution, chlorate solution, hydroxylamine salt solution, oxalic acid amine salt solution and nitrosoamine salt solution.
In the specific implementation, in the step, the dispersing agent is a hydrophobic solvent, the hydrophobic solvent is any one or a mixture of more than two of n-hexane, petroleum ether, n-pentane and n-heptane, and the adding volume of the dispersing agent is 5-100 times of the mass of the lithium iron phosphate.
In the specific implementation, in the step, the reducing agent is formaldehyde, hydrazine hydrate and NaBH 4 Any one or a mixture of more than two of ethanol, glycol and glycerol, and the molar ratio of the addition amount of the reducing agent to the noble metal is 1-10: 1.
preparation of S2 cathode active material coating
And (3) adding the optimized positive electrode material powder into N-methyl pyrrolidone solvent, conductive carbon black and polyvinylidene fluoride, uniformly mixing, coating on an aluminum foil, and drying to obtain the positive electrode plate, wherein the mass ratio of the positive electrode material powder to the conductive carbon black to the polyvinylidene fluoride is 86-97%, 2-7% and 1-7%, and the solid content of the coating slurry is 50-70%.
S3 preparation of primer coating
And adding solvent water, conductive carbon black, sodium carboxymethyl cellulose and styrene-butadiene rubber into the natural graphite powder, uniformly mixing, and coating the mixture on a copper foil, wherein the mass ratio of the graphite powder to the conductive carbon black to the sodium carboxymethyl cellulose to the styrene-butadiene rubber is 90-97%, 2-5%, 1.3-3% and 1.5-5%, and the solid content of the coating slurry is 45-70%.
S4 preparation of surface coating
Preparation of S41 surface coating material
Adding a precursor containing M and X and hexadecyl trimethyl ammonium bromide into a soluble solvent for dissolution and uniform mixing to form slurry, performing hydrothermal reaction, controlling the temperature of the hydrothermal reaction to be 200-250 ℃ and the reaction time to be 10-36 h, centrifugally filtering a product obtained after the reaction, repeatedly flushing the product with ethanol and water for multiple times, and drying to obtain a surface layer coating material;
in the specific implementation, in the step, the precursor of M is any one or a mixture of more than two of ammonium molybdate, ammonium tungstate, ammonium niobate oxalate hydrate, ammonium rhenate and alkanolamine titanate; the precursor of X is any one or a mixture of more than two of thiourea, thioacetamide and selenourea; and the molar ratio of the precursor of M to the precursor of X is 1: 5-20.
S42 application of top coating
Adding solvent water, conductive carbon black, carbon nano tube, sodium carboxymethyl cellulose and acrylic acid into the prepared surface coating material, uniformly mixing, coating the mixture on the surface coating, and drying to obtain a negative plate, wherein the mass ratio of the surface coating material to the conductive carbon black to the carbon nano tube to the sodium carboxymethyl cellulose to the acrylic acid is 87.5-97%, 1.5-5%, 0.1-2%, 0.7-2.5% and 0.7-3%, and the solid content of the coating slurry is 45-70%;
s5 preparation of battery cell
And sequentially rolling, cutting, laminating, welding tabs, sealing, injecting liquid, forming and separating the prepared positive and negative plates to obtain the low-temperature lithium ion battery, wherein the electrolyte solvent in the liquid injection procedure is ethylene carbonate and dimethyl carbonate with the volume ratio of 1:1, and the electrolyte is lithium hexafluorophosphate with the molar concentration of 0.5-1.5 mol/L.
Furthermore, the preparation method of the low-temperature lithium ion battery can reduce the reaction energy barrier by forming the noble metal layer on the surface of the lithium iron phosphate through in-situ reduction, greatly promote the deintercalation rate of lithium ions from the lithium iron phosphate anode material and the migration rate of lithium ions in the solid material at low temperature, and simultaneously, after the transition metal chalcogenide is formed on the surface of the graphite carbon layer, the rapid ion channel of the chalcogenide and the excellent conductivity advantage of the carbon material are combined, and the formed structure has an expansion layer, so that the diffusion capability of lithium ions can be further enhanced, thereby leading to better low-temperature cycle performance and multiplying power performance.
The foregoing is a complete disclosure of the present invention regarding a low temperature lithium ion battery and a method for manufacturing the same, and for better understanding and implementation, the present invention will be further described with reference to specific examples.
Example 1
The preparation method of the low-temperature lithium ion battery comprises the following steps:
(1) Adding a proper amount of commercial lithium iron phosphate powder into normal hexane solution, and stirring for 0.5h, wherein the volume of the normal hexane solution is 50 times of the mass of the lithium iron phosphate powder; adding a platinum nitrate solution into a normal hexane solution, and stirring for 1h, wherein the addition amount of a platinum simple substance accounts for 0.5% of the mass of the lithium iron phosphate; ethylene glycol is added, and the molar ratio of the ethylene glycol to the platinum simple substance is 2:1, heating to 80 ℃, continuously stirring for 3 hours, centrifugally filtering the slurry, then drying for 5 hours at 75 ℃, and continuously roasting for 6 hours at 200 ℃ to obtain optimized positive electrode material powder (LFP-A);
(2) Taking optimized positive electrode material powder (LFP-A), adding a certain amount of solvent N-methyl pyrrolidone (NMP), conductive carbon black (SP) and polyvinylidene fluoride (PVDF), uniformly mixing, coating on an aluminum foil, and drying to obtain a positive electrode plate, wherein the mass ratio of LFP-A, SP to PVDF is 95%, 2.5% and 2.5%, and the solid content of the coating slurry is 60%;
(3) Taking natural graphite powder (C), adding a certain amount of solvent water, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR), uniformly mixing, and coating on a copper foil, wherein the mass ratio of the C, the SP, the CMC and the SBR is 95%, 2%, 1.3% and 1.7%, the solid content of coating slurry is 55%, the coating thickness is 100um, and the median particle size is 10um;
(41) Adding a proper amount of ammonium molybdate, thiourea and hexadecyl trimethyl ammonium bromide into a soluble solvent for dissolution, wherein the molar ratio of the ammonium molybdate to the thiourea is 1:8, uniformly mixing the three materials to form slurry, sealing the slurry in a polytetrafluoroethylene stainless steel autoclave for hydrothermal reaction, reacting for 12 hours at 200 ℃, centrifugally filtering the obtained product, repeatedly flushing the product with ethanol and water for multiple times, and drying the product to obtain a material (B-1);
(42) Taking the material (B-1) prepared in the step (41), adding a certain amount of solvent water, conductive carbon black (SP), carbon Nanotubes (CNTs), sodium carboxymethylcellulose (CMC) and acrylic acid (PAA), uniformly mixing, coating on a surface layer coating, wherein the mass ratio of the B-1, SP, CNTs, CMC and the PAA is 94%, 2%, 0.5%, 1.5% and 2%, the solid content of coating slurry is 53%, the coating thickness is 12um, the median particle size is 50um, and drying to obtain a negative plate;
(5) Rolling the prepared positive and negative plates, cutting, laminating, welding electrode lugs, sealing to obtain single cell, injecting liquid, forming, andand (3) capacity division to obtain a soft-package battery, wherein an electrolyte solvent in the liquid injection process is ethylene carbonate: dimethyl carbonate=1:1 (volume ratio), and the electrolyte is lithium hexafluorophosphate (LiPF 6 ) The molar concentration was 1mol/L.
Example 2
The preparation method of the low-temperature lithium ion battery comprises the following steps:
(1) Adding a proper amount of commercial lithium iron phosphate powder into an n-hexane solution, and stirring for 1h, wherein the volume of the n-hexane solution is 100 times of the mass of the lithium iron phosphate powder; adding palladium dinitrate solution into normal hexane solution, stirring for 2h, wherein the addition amount of palladium simple substance is 0.8% of the mass of lithium iron phosphate; adding glycerol, wherein the mol ratio of the glycerol to the elemental palladium is 3:1, heating to 100 ℃, continuously stirring for 5 hours, centrifugally filtering the slurry, then drying for 3 hours at 100 ℃, and continuously roasting for 5 hours at 200 ℃ to obtain optimized positive electrode material powder (LFP-A);
(2) Taking optimized positive electrode material powder (LFP-A), adding a certain amount of solvent N-methyl pyrrolidone (NMP), conductive carbon black (SP) and polyvinylidene fluoride (PVDF), uniformly mixing, coating on an aluminum foil, and drying to obtain a positive electrode plate, wherein the mass ratio of LFP-A, SP to PVDF is 95%, 2.5% and 2.5%, and the solid content of the coating slurry is 60%;
(3) Taking natural graphite powder (C), adding a certain amount of solvent water, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR), uniformly mixing, and coating on a copper foil, wherein the mass ratio of the C, the SP, the CMC and the SBR is 95%, 2%, 1.3% and 1.7%, the solid content of coating slurry is 55%, the coating thickness is 100um, and the median particle size is 10um;
(41) Adding a proper amount of ammonium tungstate, thioacetamide and hexadecyl trimethyl ammonium bromide into a soluble solvent for dissolution, wherein the molar ratio of the ammonium tungstate to the thioacetamide is 1:16, uniformly mixing the three materials to form slurry, sealing the slurry in a polytetrafluoroethylene stainless steel autoclave for hydrothermal reaction, reacting for 16 hours at 220 ℃, centrifugally filtering the obtained product, repeatedly flushing the product with ethanol and water for a plurality of times, and drying the product to obtain a material (B-1);
(42) Taking the material (B-1) prepared in the step (41), adding a certain amount of solvent water, conductive carbon black (SP), carbon Nanotubes (CNTs), sodium carboxymethylcellulose (CMC) and acrylic acid (PAA), uniformly mixing, coating on a surface coating, wherein the mass ratio of the B-1, SP, CNTs, CMC to the PAA is 94.5%, 2%, 0.4%, 1.3% and 1.8%, the solid content of coating slurry is 53%, the coating thickness is 12um, the median particle size is 45um, and drying to obtain a negative plate;
(5) Respectively rolling, cutting, laminating, welding tabs and sealing the positive and negative pole pieces to obtain a single battery cell, and then injecting liquid, forming and separating to obtain a soft-packed battery, wherein the electrolyte solvent in the liquid injection process is ethylene carbonate: dimethyl carbonate=1:1 (volume ratio), and the electrolyte is lithium hexafluorophosphate (LiPF 6 ) The molar concentration was 1mol/L.
Example 3
The preparation method of the low-temperature lithium ion battery comprises the following steps:
(1) Adding a proper amount of commercial lithium iron phosphate powder into n-pentane solution, and stirring for 2 hours, wherein the volume of the n-pentane solution is 120 times of the mass of the lithium iron phosphate powder; adding a ruthenium nitrate solution into an n-pentane solution, and stirring for 3 hours, wherein the addition amount of a ruthenium simple substance accounts for 1% of the mass of the lithium iron phosphate; adding formaldehyde, wherein the mole ratio of formaldehyde to ruthenium simple substance is 5:1, heating to 75 ℃, continuously stirring for 2.5 hours, centrifugally filtering the slurry, then drying for 5 hours at 80 ℃, and continuously roasting for 6 hours at 200 ℃ to obtain optimized positive electrode material powder (LFP-A);
(2) Taking optimized positive electrode material powder (LFP-A), adding a certain amount of solvent N-methyl pyrrolidone (NMP), conductive carbon black (SP) and polyvinylidene fluoride (PVDF), uniformly mixing, coating on an aluminum foil, and drying to obtain a positive electrode plate, wherein the mass ratio of LFP-A, SP to PVDF is 95%, 2.5% and 2.5%, and the solid content of the coating slurry is 60%;
(3) Taking natural graphite powder (C), adding a certain amount of solvent water, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR), uniformly mixing, and coating on a copper foil, wherein the mass ratio of the C, the SP, the CMC and the SBR is 95%, 2%, 1.3% and 1.7%, the solid content of coating slurry is 55%, the coating thickness is 100um, and the median particle size is 10um;
(41) Adding proper amounts of ammonium rhenate, selenourea and hexadecyl trimethyl ammonium bromide into a soluble solvent for dissolution, wherein the molar ratio of the ammonium rhenate to the selenourea is 1:10, uniformly mixing the three materials to form slurry, sealing the slurry in a polytetrafluoroethylene stainless steel autoclave for hydrothermal reaction, performing reaction at 215 ℃ for 24 hours, centrifugally filtering the obtained product, repeatedly washing the obtained product with ethanol and water for multiple times, and drying the obtained product to obtain a material (B-1);
(42) Taking the material (B-1) prepared in the step (41), adding a certain amount of solvent water, conductive carbon black (SP), carbon Nanotubes (CNTs), sodium carboxymethylcellulose (CMC) and acrylic acid (PAA), uniformly mixing, coating on a surface coating, and drying to obtain a negative plate, wherein the mass ratio of the B-1, the SP, CNTs, CMC and the PAA is 94.5%, 2%, 0.4%, 1.3% and 1.8%, the solid content of coating slurry is 53%, the coating thickness is 12um, and the median particle diameter is 55um;
(5) Respectively rolling, cutting, laminating, welding tabs and sealing the positive and negative pole pieces to obtain a single battery cell, and then injecting liquid, forming and separating to obtain a soft-packed battery, wherein the electrolyte solvent in the liquid injection process is ethylene carbonate: dimethyl carbonate=1:1 (volume ratio), and the electrolyte is lithium hexafluorophosphate (LiPF 6 ) The molar concentration was 1mol/L.
Comparative example 1
The comparative example discloses a preparation method of a lithium ion battery, wherein the anode material and the cathode coating are not improved, and the anode material and the cathode coating in the prior art are adopted, and the preparation method comprises the following specific steps:
(1) And adding a certain amount of solvent N-methyl pyrrolidone (NMP), conductive carbon black (SP) and polyvinylidene fluoride (PVDF) into commercial lithium iron phosphate material powder (LFP), uniformly mixing, and coating on an aluminum foil to obtain a positive plate, wherein the mass ratio of LFP-A, SP to PVDF is 95%, 2.5% and 2.5%, the solid content of the coating slurry is 60%, and the coating surface density of the lithium iron phosphate material is consistent with that of the specific example 1.
(2) Taking natural graphite powder (C), adding a certain amount of solvent water, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR), uniformly mixing, and coating on a copper foil to obtain a negative plate, wherein the mass ratio of the C, the SP, the CMC and the SBR is 95%, 2%, 1.3% and 1.7%, the solid content of coating slurry is 55%, the coating thickness is 112um, and the median particle size is 10um;
(3) Respectively rolling, cutting, laminating, welding tabs and sealing the positive and negative pole pieces to obtain a single battery cell, and then injecting liquid, forming and separating to obtain a soft-packed battery, wherein the electrolyte solvent in the liquid injection process is ethylene carbonate: dimethyl carbonate=1:1 (volume ratio), and the electrolyte is lithium hexafluorophosphate (LiPF 6 ) The molar concentration was 1mol/L.
Comparative example 2
The comparative example discloses a preparation method of a lithium ion battery, wherein a positive electrode material is improved, a negative electrode coating is not improved, namely the negative electrode coating is prepared by adopting the prior art, and the positive electrode coating is prepared by adopting the technical scheme of the invention, and the specific steps are as follows:
(1) Adding a proper amount of commercial lithium iron phosphate powder into normal hexane solution, and stirring for 0.5h, wherein the volume of the normal hexane solution is 50 times of the mass of the lithium iron phosphate powder; adding a platinum nitrate solution into a normal hexane solution, and stirring for 1h, wherein the addition amount of a platinum simple substance accounts for 0.5% of the mass of the lithium iron phosphate; ethylene glycol is added, and the mole ratio of the ethylene glycol to the simple substance platinum is 2:1, heating to 80 ℃, continuously stirring for 3 hours, centrifugally filtering the slurry, then drying at 75 ℃ for 5 hours, and continuously roasting at 200 ℃ for 6 hours to obtain optimized positive electrode material powder (LFP-A);
(2) Taking optimized positive electrode material powder (LFP-A), adding a certain amount of solvent N-methyl pyrrolidone (NMP), conductive carbon black (SP) and polyvinylidene fluoride (PVDF), uniformly mixing, and coating on an aluminum foil to obtain a positive electrode plate, wherein the mass ratio of LFP-A, SP to PVDF is 95%, 2.5% and 2.5%, and the solid content of the coating slurry is 60%;
(3) Taking natural graphite powder (C), adding a certain amount of solvent water, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR), uniformly mixing, and coating on a copper foil to obtain a negative plate, wherein the mass ratio of the C, the SP, the CMC and the SBR is 95%, 2%, 1.3% and 1.7%, the solid content of coating slurry is 55%, the coating thickness is 112um, and the median particle size is 10um;
(4) Respectively rolling, cutting, laminating, welding tabs and sealing the positive and negative pole pieces to obtain a single battery cell, and then injecting liquid, forming and separating to obtain a soft-packed battery, wherein the electrolyte solvent in the liquid injection process is ethylene carbonate: dimethyl carbonate=1:1 (volume ratio), and the electrolyte is lithium hexafluorophosphate (LiPF 6 ) The molar concentration was 1mol/L.
Comparative example 3
The comparative example discloses a preparation method of a lithium ion battery, wherein a positive electrode material is not improved, a negative electrode coating is improved, namely the positive electrode coating is prepared by adopting the prior art, the negative electrode coating is prepared by adopting the technical scheme of the invention, and the specific steps are as follows:
(1) Taking commercial lithium iron phosphate material powder (LFP), adding a certain amount of solvent N-methylpyrrolidone (NMP), conductive carbon black (SP) and polyvinylidene fluoride (PVDF), uniformly mixing, and coating on an aluminum foil to obtain a positive plate, wherein the mass ratio of LFP-A, SP to PVDF is 95%, 2.5% and 2.5%, the solid content of coating slurry is 60%, and the coating surface density of the lithium iron phosphate material is consistent with that of the specific example 1;
(2) Taking natural graphite powder (C), adding a certain amount of solvent water, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR), uniformly mixing, and coating on a copper foil, wherein the mass ratio of the C, the SP, the CMC and the SBR is 95%, 2%, 1.3% and 1.7%, the solid content of coating slurry is 55%, the coating thickness is 100um, and the median particle size is 10um;
(31) Adding a proper amount of ammonium molybdate, thiourea and hexadecyl trimethyl ammonium bromide into a soluble solvent for dissolution, wherein the molar ratio of the ammonium molybdate to the thiourea is 1:8, uniformly mixing the three materials to form slurry, sealing the slurry in a polytetrafluoroethylene stainless steel autoclave for hydrothermal reaction, reacting for 12 hours at 200 ℃, centrifugally filtering the obtained product, repeatedly flushing the product with ethanol and water for multiple times, and drying the product to obtain a material (B-1);
(32) Taking the material (B-1) prepared in the step (31), adding a certain amount of solvent water, conductive carbon black (SP), carbon Nanotubes (CNTs), sodium carboxymethylcellulose (CMC) and acrylic acid (PAA), uniformly mixing, and coating on a surface coating to obtain a negative plate, wherein the mass ratio of the B-1, the SP, CNTs, CMC and the PAA is 94%, 2%, 0.5%, 1.5% and 2%, the solid content of coating slurry is 53%, the coating thickness is 12um, and the median particle size is 50um;
(4) Rolling, cutting, laminating, welding electrode lugs and sealing the positive electrode plate and the negative electrode plate to obtain a single battery cell, and injecting liquid, forming and separating to obtain a soft-package battery, wherein the electrolyte solvent in the liquid injection process is ethylene carbonate: dimethyl carbonate=1:1 (volume ratio), and the electrolyte is lithium hexafluorophosphate (LiPF 6 ) The molar concentration was 1mol/L.
The batteries prepared in specific examples 1 to 3 and comparative examples 1 to 3 were subjected to a low temperature cycle test and a low temperature rate test:
low temperature cycle test:
the corresponding battery is fully charged (0.1C constant current is charged to 3.65V at normal temperature (25 ℃), then constant voltage is charged to cut-off current smaller than 0.02C), discharging is carried out at low temperature (-10 ℃ or-20 ℃), discharging is carried out at 0.1C constant current to 2.5V respectively, circulation is carried out for 100 times, and the discharge capacity retention rate is calculated, so that the following data are obtained:
table low temperature cycle performance data summary table of battery corresponding to example and comparative example
As can be seen from the data in table one:
in general, the order of decrease in the discharge capacity retention rate of the battery after 100 cycles at-10 ℃ or-20 ℃ was specific example 1≡specific example 2≡specific example 3> comparative example 2≡comparative example 3> comparative example 1, that is, the battery prepared in specific examples 1 to 3 had the slowest and least decrease rate of the capacity, and the battery prepared in comparative example 2 and comparative example 3 were inferior, and the battery prepared in comparative example 1 had the fastest and most decrease rate.
From this, after the positive electrode material or the negative electrode coating is improved in the invention, the low-temperature performance of the lithium iron phosphate battery at low temperature can be improved: after the anode material is improved, a noble metal layer is formed on the surface of the lithium iron phosphate in an in-situ reduction manner, the noble metal has good dispersibility on the surface of a lithium iron phosphate carrier, a good catalytic effect is achieved, the reaction energy barrier is reduced at a low temperature, and the deintercalation rate and the migration rate of lithium ions in the lithium iron phosphate anode material are greatly promoted; when the anode coating is improved, the transition metal chalcogenide on the surface layer of the anode coating has a two-dimensional layered structure, and the formed structure has an expansion layer after being coated on the surface of the graphite carbon layer, so that the diffusion capability of lithium ions can be further enhanced.
It can thus also be verified that: comparative example 2 and comparative example 3 improved only the active components on the positive and negative electrode sides, and thus had lower performance than the battery prepared in comparative example 1, which was not improved, and were inferior to the batteries prepared in specific comparative examples 1 to 3, which were improved in both positive and negative electrodes.
Low temperature rate test:
the corresponding battery is tested at-20 ℃, and the testing method comprises the following steps: fully charging at normal temperature (25 ℃) (0.1C constant current is charged to 3.65V, then constant voltage is charged to cut-off current is smaller than 0.02C), discharging to 2.5V at different multiplying power, charging and discharging are carried out for 5 times at each multiplying power cycle, capacity retention rates at 0.5C, 1C and 2C are tested in sequence, and finally capacity at 0.5C is tested again, capacity recovery rate at 0.5C is calculated, and a low-temperature multiplying power performance data summary table and a graph of FIG. 1 are obtained;
and (II) table: rate performance data summary table of battery corresponding to examples and comparative examples
As can be seen from fig. 1 and table two:
the capacity retention rate of the battery at different rates and the capacity recovery rate performance of 0.5C at-20 ℃ are:
the batteries prepared in specific examples 1, 2 and 3 are optimal, and comparative examples 2 and 3 are worst, and comparative example 1 shows that after the anode material is improved, a noble metal layer is formed on the surface of the lithium iron phosphate by in-situ reduction, the noble metal has good dispersibility on the surface of a lithium iron phosphate carrier, has good catalytic action, reduces the reaction energy barrier at low temperature, greatly promotes the deintercalation rate and migration rate of lithium ions in the lithium iron phosphate anode material, reduces the internal diffusion resistance of lithium ions among solid particles, and improves the charge and discharge performance under large current; and after the anode coating is improved, the transition metal chalcogenide on the surface layer of the anode coating can enhance the diffusion capacity of lithium ions, and meanwhile, as the two-dimensional transition metal chalcogenide has better electrocatalytic performance and rich surface, subsurface and edge structures, the desolvation process of the lithium ions at the interface of the graphite anode and electrolyte is promoted, namely, the electrochemical impedance and diffusion impedance of the lithium ions are reduced, the polarization in the lithium ion battery is reduced, and the low-temperature rate performance is improved.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (9)

1. The low-temperature lithium ion battery consists of a positive plate, a negative plate, a diaphragm and electrolyte, and is characterized in that a positive active material coating of the positive plate is lithium iron phosphate with a noble metal layer attached to the surface, a negative active material coating of the negative plate is a double coating, wherein a middle bottom coating of the double coating is graphite, and a surface coating is a transition metal sulfur compound;
the preparation method of the low-temperature lithium ion battery comprises the following steps:
preparation of S1 cathode active Material
Adding lithium iron phosphate powder into a dispersing agent, and stirring for 0.5-2 h;
adding a noble metal salt solution into a dispersing agent containing lithium iron phosphate powder, and stirring for 1-3 hours;
adding a reducing agent, heating to 60-110 ℃, stirring for 1-6 hours, centrifuging, filtering, drying at 60-120 ℃ for 3-10 hours, and roasting at 200 ℃ for 5-8 hours to obtain optimized anode material powder;
preparation of S2 cathode active material coating
The optimized positive electrode material powder is taken, N-methyl pyrrolidone solvent, conductive carbon black and polyvinylidene fluoride are added, and uniformly mixed, and then the mixture is coated on an aluminum foil, and the positive electrode plate is obtained after drying, wherein the mass ratio of the positive electrode material powder to the conductive carbon black to the polyvinylidene fluoride is 86-97%, 2-7% and 1-7%, and the solid content of the coating slurry is 50-70%;
s3 preparation of primer coating
Adding solvent water, conductive carbon black, sodium carboxymethyl cellulose and styrene-butadiene rubber into natural graphite powder, uniformly mixing, and coating the mixture on a copper foil, wherein the mass ratio of the graphite powder to the conductive carbon black to the sodium carboxymethyl cellulose to the styrene-butadiene rubber is 90-97%, 2-5%, 1.3-3% and 1.5-5%, and the solid content of the coating slurry is 45-70%;
s4 preparation of surface coating
Preparation of S41 surface coating material
Adding a precursor containing M and X and hexadecyl trimethyl ammonium bromide into a soluble solvent for dissolution and uniform mixing to form slurry, performing hydrothermal reaction, controlling the temperature of the hydrothermal reaction to be 200-250 ℃ and the reaction time to be 10-36 h, centrifugally filtering a product obtained after the reaction, repeatedly flushing the product with ethanol and water for multiple times, and drying to obtain a surface layer coating material;
s42 application of top coating
Adding solvent water, conductive carbon black, carbon nano tube, sodium carboxymethyl cellulose and acrylic acid into the prepared surface coating material, uniformly mixing, coating the mixture on the surface coating, and drying to obtain a negative plate, wherein the mass ratio of the surface coating material to the conductive carbon black to the carbon nano tube to the sodium carboxymethyl cellulose to the acrylic acid is 87.5-97%, 1.5-5%, 0.1-2%, 0.7-2.5% and 0.7-3%, and the solid content of the coating slurry is 45-70%;
s5 preparation of battery cell
And sequentially rolling, cutting, laminating, welding tabs, sealing, injecting liquid, forming and separating the prepared positive and negative plates to obtain the low-temperature lithium ion battery, wherein the electrolyte solvent in the liquid injection procedure is ethylene carbonate and dimethyl carbonate with the volume ratio of 1:1, and the electrolyte is lithium hexafluorophosphate with the molar concentration of 0.5-1.5 mol/L.
2. The low-temperature lithium ion battery according to claim 1, wherein the coating thickness ratio of the bottom coating layer and the surface coating layer of the negative electrode sheet is 5-20: 1, a step of; and the particle size of graphite is 5-30um, and the particle size of the transition metal chalcogenide is 35-80 um.
3. The low-temperature lithium ion battery according to claim 1, wherein the noble metal element of the noble metal layer is any one or a mixture of any two or more of platinum, palladium, rhodium, ruthenium, iridium and osmium, and the content of the noble metal is 0.2-5% of the mass of the lithium iron phosphate.
4. The low temperature lithium ion battery of claim 1, wherein the transition metal chalcogenide has the formula MX 2 C; wherein M is a transition metal element, and X is a chalcogen element.
5. The low-temperature lithium ion battery according to claim 4, wherein the transition metal element is any one or a mixture of any two or more of molybdenum, tungsten, niobium, titanium and rhenium, and the chalcogen element is any one or a mixture of any two or more of sulfur, selenium and tellurium.
6. The low-temperature lithium ion battery according to claim 1, wherein in the step S1, the noble metal salt solution is any one or a mixture of two or more of a nitrate solution, a chlorate solution, a hydroxylamine salt solution, an oxalic acid amine salt solution and a nitrosoamine salt solution.
7. The low-temperature lithium ion battery according to claim 1, wherein in the step S1, the dispersing agent is a hydrophobic solvent, the hydrophobic solvent is any one or a mixture of any two or more of n-hexane, petroleum ether, n-pentane and n-heptane, and the adding volume amount of the dispersing agent is 5-100 times of the mass of the lithium iron phosphate.
8. The low-temperature lithium ion battery according to claim 1, wherein in the step S1, the reducing agent is formaldehyde, hydrazine hydrate, naBH 4 Any one or a mixture of more than two of ethanol, glycol and glycerol, and the molar ratio of the addition amount of the reducing agent to the noble metal is 1-10: 1.
9. the low-temperature lithium ion battery according to claim 1, wherein in the step S41, the precursor of M is any one or a mixture of any two or more of ammonium molybdate, ammonium tungstate, ammonium niobate oxalate hydrate, ammonium rhenate, alkanolamine titanate; the precursor of X is any one or a mixture of more than two of thiourea, thioacetamide and selenourea; and the molar ratio of the precursor of M to the precursor of X is 1: 5-20.
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