CN113380971A - Composite negative electrode material of thin-film lithium ion battery and preparation method thereof - Google Patents
Composite negative electrode material of thin-film lithium ion battery and preparation method thereof Download PDFInfo
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- 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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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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Abstract
The invention provides a preparation method of a composite cathode material of a film lithium ion battery, which comprises the following steps: dissolving lithium salt, aluminum nitrate and phosphorus-containing compound in solvent, and then dripping organic titanium compound to obtain Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Precursor solution of the Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3The ratio of the amount of lithium, aluminum, titanium and phosphorus in the precursor solution is (3.53-3.953): (0.03-0.003) (4.42-4.942) (0.3-0.03); subjecting the Li to4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Depositing the precursor solution on a substrate, and carrying out heat treatment on the substrate at the temperature of 400-450 ℃ for 10-12 minutes to obtain a material matrix; soaking the material intermediate in 0.2-0.3mol/L silver nitrate solution for 1-5 minutes, taking out, and then performing heat treatment at the temperature of 700-850 ℃ for 2-30 minutes to obtain the material intermediate, wherein the content of silver element in the material intermediate is 0.5-5%; and (3) evaporating a 1-3 mu m Mo layer on the surface of the material intermediate body to obtain the thin-film lithium ion battery composite negative electrode material. The invention also provides a composite cathode material of the film lithium ion battery. The composite negative electrode material of the film lithium ion battery provided by the invention has small internal resistance.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of lithium ion batteries, in particular to a thin-film lithium ion battery composite negative electrode material and a preparation method thereof.
[ background of the invention ]
The lithium ion battery has the advantages of high energy density, long cycle life, stable working voltage, low self-discharge, no memory effect, small pollution and the like, so that the lithium ion battery is rapidly developed and widely applied and becomes a secondary battery with the most extensive application. The all-solid-state thin-film lithium ion battery is used as a branch of the lithium ion battery, all components in the battery structure exist in a solid state form and are formed by overlapping compact positive electrode films, electrolyte films and negative electrode films on a substrate, the all-solid-state thin-film lithium ion battery has extremely high safety, the solid electrolyte of the all-solid-state thin-film lithium ion battery is nonflammable, non-corrosive, non-volatile and liquid-tight, meanwhile, the dendritic lithium phenomenon is overcome, and the spontaneous combustion probability of an automobile carrying the all-solid-state lithium battery is greatly reduced.
In the related art, the thin film lithium ion battery has large internal resistance (more prominent when the thickness of an electrode thin film is increased), which hinders the application and development of the thin film battery. The internal resistance of the thin-film battery depends on the resistance of the positive and negative thin films to a great extent, and the reason for the large resistance of the positive and negative thin films mainly includes two points: compared with the conventional lithium ion battery electrode, the carbon black electronic conductive agent is lacked in the positive electrode and the negative electrode of the thin film battery, so that the electronic conductivity of the electrode thin film is lower; on the other hand, the thin film battery uses a solid electrolyte, which cannot be impregnated into the electrode as a liquid electrolyte, resulting in a low ionic conductivity of the electrode thin film. Therefore, there is a need to provide a composite negative electrode material for a thin film lithium ion battery and a preparation method thereof to solve the above problems.
[ summary of the invention ]
The invention discloses a composite cathode material of a thin-film lithium ion battery and a preparation method thereof, which aim to reduce the internal resistance of the thin-film battery.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a composite cathode material of a thin-film lithium ion battery comprises the following steps:
s1: dissolving lithium salt, aluminum nitrate and phosphorus-containing compound in solvent, and then dripping organic titanium compound to obtain Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Precursor solution of the Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3The ratio of the amount of lithium, aluminum, titanium and phosphorus in the precursor solution is (3.53-3.953): (0.03-0.003): 4.42-4.942): 0.3-0.03);
s2: the Li is subjected to spray pyrolysis or spin coating technology4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Depositing the precursor solution on a substrate, and carrying out heat treatment on the substrate at the temperature of 400-450 ℃ for 10-12 minutes to obtain a material matrix;
s3: soaking the material intermediate in 0.2-0.3mol/L silver nitrate solution for 1-5 minutes, taking out, and then performing heat treatment at the temperature of 700-850 ℃ for 2-30 minutes to obtain the material intermediate, wherein the content of silver element in the material intermediate is 0.5-5%;
s4: and (3) evaporating a 1-3 mu m Mo layer on the surface of the material intermediate body to obtain the thin-film lithium ion battery composite negative electrode material.
Preferably, the solvent is ethanol or ethylene glycol methyl ether.
Preferably, the lithium salt is lithium acetate or lithium nitrate.
Preferably, the titanium organic compound is a titanate.
Preferably, the titanium organic compound is tetrabutyl titanate or isopropyl titanate.
Preferably, the phosphorus-containing compound is ammonium dihydrogen phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate or tributyl phosphate.
Preferably, the substrate is a silicon wafer, a platinized silicon wafer or a lithium ion solid electrolyte Li1.3Al0.3Ti1.7(PO4)3And sintering the sheet.
The invention also provides a film lithium ion battery composite negative electrode material prepared by the preparation method.
Preferably, the thickness of the composite negative electrode material of the thin-film lithium ion battery is less than 100 μm.
Compared with the prior art, the Li can be obtained by adopting soluble lithium salt, aluminum nitrate, titanium organic compound and phosphorus-containing compound as raw materials in proper proportion and controlling the synthesis conditions4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3And finally, plating a Mo/Ag composite plating layer on the material matrix. Due to Li1.3Al0.3Ti1.7(PO4)3Is an excellent lithium ion conductor, the Mo/Ag composite coating is an excellent electronic conductor, and the prepared Li4Ti5O12The thin film contains Li1.3Al0.3Ti1.7(PO4)3And the Mo/Ag composite coating can improve Li at the same time4Ti5O12Ion and electron conductivity of the film, reduction of Li4Ti5O12The film resistance is beneficial to preparing the low-resistance film lithium ion battery.
[ detailed description ] embodiments
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The invention provides a preparation method of a composite cathode material of a film lithium ion battery, which comprises the following steps:
s1: dissolving lithium salt, aluminum nitrate and phosphorus-containing compound in solvent, and then dripping organic titanium compound to obtain Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Precursor solution of the Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3The ratio of the amount of lithium, aluminum, titanium and phosphorus in the precursor solution is (3.53-3.953): (0.03-0.003): 4.42-4.942): 0.3-0.03.
Lithium and titanium can react to form Li4Ti5O12And Li, Al, Ti and P may react to form Li1.3Al0.3Ti1.7(PO4)3Therefore, by appropriately controlling the amount ratio of lithium, aluminum, titanium, and phosphorus and the reaction conditions, Li can be produced simultaneously4Ti5O12With Li1.3Al0.3Ti1.7(PO4)3，Li4Ti5O12As a negative electrode material of a lithium ion battery, can be mixed with LiMn2O4、LiCoO2And the 4V-grade anode material is used for forming the lithium ion battery with the working voltage of 2.4V. Li4Ti5O12The intercalation and deintercalation of lithium ions in the process of charging and discharging have little influence on the material structure, are called zero-strain materials, and are ideal cathode materials of solid film lithium ion batteries.
Preferably, the solvent is ethanol or ethylene glycol methyl ether; the lithium salt is lithium acetate or lithium nitrate; the titanium organic compound is titanate; the titanium organic compound is tetrabutyl titanate or isopropyl titanate; the phosphorus-containing compound is ammonium dihydrogen phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate or tributyl phosphate; the substrate is a silicon wafer, a platinized silicon wafer or a lithium ion solid electrolyte Li1.3Al0.3Ti1.7(PO4)3And sintering the sheet.
S2: the Li is subjected to spray pyrolysis or spin coating technology4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Depositing the precursor solution on a substrate, and carrying out heat treatment on the substrate at the temperature of 400-450 ℃ for 10-12 minutes to obtain the material matrix.
S3: and (2) soaking the material intermediate in 0.2-0.3mol/L silver nitrate solution for 1-5 minutes, taking out, and then performing heat treatment at the temperature of 700-850 ℃ for 2-30 minutes to obtain the material intermediate, wherein the content of the silver element in the material intermediate is 0.5-5%.
During the soaking process, silver nitrate solution is attached to the surface of the material matrix, and under the high-temperature condition, because silver nitrate cannot enter Li4Ti5O12And Li1.3Al0.3Ti1.7(PO4)3And the silver nitrate is decomposed into simple substance silver to be attached to the surface of the material matrix when being heated at high temperature.
S4: and (3) evaporating a 1-3 mu m Mo layer on the surface of the material intermediate body to obtain the thin-film lithium ion battery composite negative electrode material.
Because the evaporation temperature of Mo is higher than the melting temperature of silver, in the evaporation process, the high-temperature gasified Mo particles can re-melt the silver layer on the surface of the material matrix and combine with Mo to form a composite coating, thereby increasing the adhesive force of the composite coating and the material matrix. And the addition of Mo can also increase the strength and toughness of the plating layer and prolong the service life of the cathode.
Due to Li1.3Al0.3Ti1.7(PO4)3Is an excellent lithium ion conductor, and the molybdenum silver coating is an excellent electronic conductor, so that the prepared film lithium ion battery composite cathode material can improve Li at the same time4Ti5O12Ion and electron conductivity of the film, reduction of Li4Ti5O12A sheet resistance.
The invention also provides a film lithium ion battery composite negative electrode material prepared by the preparation method.
Preferably, the thickness of the composite negative electrode material of the thin-film lithium ion battery is less than 100 μm.
Example 1
Weighing 1.9765 mol of acetic acidDissolving lithium, 0.0015g mol of aluminum nitrate and 0.015g mol of tributyl phosphate in 1000 ml of ethanol, fully stirring, and after all solutes are dissolved completely, dripping 2.471 mol of isopropyl titanate into the mixed solution under the condition of continuous stirring to obtain Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Precursor solution;
spray pyrolysis method is adopted to lead Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Deposition of precursor solution on Li1.3Al0.3Ti1.7(PO4)3Sintering the sheet at 380 deg.C, spraying nozzle and Li1.3Al0.3Ti1.7(PO4)3The distance between the solid electrolyte sintered sheets is 8cm, and the deposited film is subjected to heat treatment at 800 ℃ for 10 minutes to obtain a material matrix;
placing the material matrix into 0.2mol/L silver nitrate solution to be soaked for 1 minute, taking out the material matrix, and then placing the material matrix at the temperature of 700 ℃ to be subjected to heat treatment for 2 minutes to obtain a material intermediate, wherein the content of silver element in the material intermediate is 0.5%;
and (3) evaporating a 1-micron Mo layer on the surface of the material intermediate to obtain the film lithium ion battery composite negative electrode material.
The thickness of the thin film lithium ion battery composite negative electrode material is 20 mu m, and Li in the thin film lithium ion battery composite negative electrode material4Ti5O12、Li1.3Al0.3Ti1.7(PO4)3The amount ratio of Ag material was 0.985:0.01: 0.005.
Example 2
1.765 mol of lithium acetate, 0.015 mol of aluminum nitrate and 0.15 mol of ammonium dihydrogen phosphate are weighed and dissolved in 1000 ml of ethylene glycol monomethyl ether, then 5 ml of concentrated nitric acid is dripped, the mixture is fully stirred, and 2.21 mol of tetrabutyl titanate is dripped into the mixed solution under the condition of continuous stirring after all solutes are dissolved to obtain Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Precursor solution；
Li is coated by spin coating4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Deposition of precursor solution on Li1.3Al0.3Ti1.7(PO4)3Obtaining a wet film on a sintering sheet, heating the obtained wet film to 350 ℃ in air at a heating rate of 10 ℃/min for 20 minutes, then repeatedly carrying out rotary coating and heating decomposition to obtain a film with required thickness, and finally carrying out heat treatment in an air atmosphere at 800 ℃ for 5 minutes to obtain a material substrate;
placing the material matrix into 0.25mol/L silver nitrate solution to be soaked for 2 minutes, taking out the material matrix, and then placing the material matrix at the temperature of 800 ℃ to be subjected to heat treatment for 20 minutes to obtain a material intermediate, wherein the content of silver element in the material intermediate is 5%;
and (3) evaporating a 2-micron Mo layer on the surface of the material intermediate to obtain the film lithium ion battery composite negative electrode material.
The thickness of the thin film lithium ion battery composite negative electrode material is 30 mu m, and Li in the thin film lithium ion battery composite negative electrode material4Ti5O12、Li1.3Al0.3Ti1.7(PO4)3The amount ratio of Ag substance was 0.85:0.1: 0.05.
Example 3
Weighing 1.752 mol of lithium acetate, 0.012 mol of aluminum nitrate and 0.12 mol of ammonium dihydrogen phosphate, dissolving in 1000 ml of ethanol, then dropwise adding 5 ml of concentrated nitric acid, fully stirring, and after all solutes are dissolved, dropwise adding 2.318 mol of tetrabutyl titanate into the mixed solution under the condition of continuous stirring to obtain Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Precursor solution;
li is coated by spin coating4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Depositing the precursor solution on a silicon wafer to obtain a wet film, heating the wet film to 380 ℃ in air at a heating rate of 10 ℃/min for 20 minutes, and repeating the stepsPerforming rotary coating and thermal decomposition to obtain a film with required thickness, and finally performing heat treatment at 800 ℃ for 5 minutes in an air atmosphere to obtain a material matrix;
placing the material matrix into 0.3mol/L silver nitrate solution to be soaked for 5 minutes, taking out the material matrix, and then placing the material matrix at 850 ℃ to be subjected to heat treatment for 30 minutes to obtain a material intermediate, wherein the content of silver element in the material intermediate is 2%;
and (3) evaporating a 1-micrometer Mo layer on the surface of the material intermediate to obtain the film lithium ion battery composite negative electrode material, wherein the content of silver in the film lithium ion battery composite negative electrode material is 2%.
The thickness of the thin film lithium ion battery composite negative electrode material is 8 mu m, and Li in the thin film lithium ion battery composite negative electrode material4Ti5O12、Li1.3Al0.3Ti1.7(PO4)3The amount ratio of Ag substance was 0.9:0.08: 0.02.
Example 4
1.8925 mol of lithium acetate, 0.0075 mol of aluminum nitrate and 0.075 mol of tributyl phosphate are weighed and dissolved in 1000 ml of ethanol, the mixture is fully stirred, and after all solutes are dissolved, 2.3675 mol of tetrabutyl titanate is dripped into the mixed solution under the condition of continuous stirring to obtain Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Precursor solution;
spraying Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3The precursor solution is deposited on a platinized silicon wafer, the temperature of the platinized silicon wafer is controlled at 400 ℃, and a nozzle and Li are mixed1.3Al0.3Ti1.7(PO4)3The distance between the solid electrolyte sintering sheets is 8cm, and finally the deposited film is subjected to heat treatment for 5 minutes at 800 ℃ in air atmosphere to obtain a material matrix;
placing the material matrix into a silver nitrate solution to be soaked for 4 minutes, taking out the material matrix, and then placing the material matrix at the temperature of 700 ℃ to be subjected to heat treatment for 18 minutes to obtain a material intermediate, wherein the content of silver element in the material intermediate is 2%;
and (3) evaporating a 3-micrometer Mo layer on the surface of the material intermediate body to obtain the thin-film lithium ion battery composite negative electrode material.
The thickness of the thin film lithium ion battery composite negative electrode material is 10 mu m, and Li in the thin film lithium ion battery composite negative electrode material4Ti5O12、Li1.3Al0.3Ti1.7(PO4)3The amount ratio of Ag substance was 0.93:0.05: 0.02.
Compared with the prior art, the Li can be obtained by adopting soluble lithium salt, aluminum nitrate, titanium organic compound and phosphorus-containing compound as raw materials in proper proportion and controlling the synthesis conditions4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3And finally, plating a Mo/Ag composite plating layer on the material matrix. Due to Li1.3Al0.3Ti1.7(PO4)3Is an excellent lithium ion conductor, the Mo/Ag composite coating is an excellent electronic conductor, and the prepared Li4Ti5O12The thin film contains Li1.3Al0.3Ti1.7(PO4)3And the Mo/Ag composite coating can improve Li at the same time4Ti5O12Ion and electron conductivity of the film, reduction of Li4Ti5O12The film resistance is beneficial to preparing the low-resistance film lithium ion battery.
Claims (9)
1. A preparation method of a composite cathode material of a thin-film lithium ion battery is characterized by comprising the following steps:
s1: dissolving lithium salt, aluminum nitrate and phosphorus-containing compound in solvent, and then dripping organic titanium compound to obtain Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Precursor solution of the Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3The ratio of the amount of lithium, aluminum, titanium and phosphorus in the precursor solution is (3.53-3.953): (0.03-0.003): 4.42-4.942): 0.3-0.03);
s2: the Li is subjected to spray pyrolysis or spin coating technology4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3Depositing the precursor solution on a substrate, and carrying out heat treatment on the substrate at the temperature of 400-450 ℃ for 10-12 minutes to obtain a material matrix;
s3: soaking the material intermediate in 0.2-0.3mol/L silver nitrate solution for 1-5 minutes, taking out, and then performing heat treatment at the temperature of 700-850 ℃ for 2-30 minutes to obtain the material intermediate, wherein the content of silver element in the material intermediate is 0.5-5%;
s4: and (3) evaporating a 1-3 mu m Mo layer on the surface of the material intermediate body to obtain the thin-film lithium ion battery composite negative electrode material.
2. The preparation method of the thin-film lithium ion battery composite anode material according to claim 1, wherein the solvent is ethanol or ethylene glycol monomethyl ether.
3. The method for preparing the thin-film lithium ion battery composite anode material according to claim 1, wherein the lithium salt is lithium acetate or lithium nitrate.
4. The method for preparing the thin-film lithium ion battery composite anode material according to claim 1, wherein the titanium organic compound is titanate.
5. The preparation method of the thin-film lithium ion battery composite anode material according to claim 4, wherein the titanium organic compound is tetrabutyl titanate or isopropyl titanate.
6. The method of claim 1, wherein the phosphorus-containing compound is ammonium dihydrogen phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, or tributyl phosphate.
7.The preparation method of the thin-film lithium ion battery composite anode material according to claim 1, wherein the substrate is a silicon wafer, a platinized silicon wafer or a lithium ion solid electrolyte Li1.3Al0.3Ti1.7(PO4)3And sintering the sheet.
8. The composite negative electrode material of the thin-film lithium ion battery is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The thin-film lithium ion battery composite anode material of claim 8, wherein the thickness of the thin-film lithium ion battery composite anode material is less than 100 μm.
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