CN112635720B - Electrode material lithium supplement additive, preparation method and application thereof, and lithium ion battery - Google Patents

Electrode material lithium supplement additive, preparation method and application thereof, and lithium ion battery Download PDF

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CN112635720B
CN112635720B CN201910953234.0A CN201910953234A CN112635720B CN 112635720 B CN112635720 B CN 112635720B CN 201910953234 A CN201910953234 A CN 201910953234A CN 112635720 B CN112635720 B CN 112635720B
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lithium
supplement additive
electrode material
lithium supplement
additive
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CN112635720A (en
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孙赛
张丝雨
高焕新
张同宝
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to the field of lithium ion batteries, and discloses an electrode material lithium supplement additive, a preparation method and an application thereof, and a lithium ion battery. The preparation method of the lithium supplement additive for the electrode material comprises the following steps: mixing a polymer lithium salt, a carbon source and a solvent; (2) Carrying out solid-liquid separation on the materials obtained by mixing in the step (1); (3) And carrying out heat treatment on the solid substance obtained by the solid-liquid separation. The lithium supplement additive for the electrode material provided by the invention is convenient to store, has no special requirements on the use working condition, and can improve the specific capacity of the material when being used in the electrode material.

Description

Electrode material lithium supplement additive, preparation method and application thereof, and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an electrode material lithium supplement additive, a preparation method and application thereof and a lithium ion battery.
Background
The theoretical specific capacity of the silicon base material is 4200 mA.h.g -1 The lithium ion battery is a cathode material with the highest gram capacity at present, and once the lithium ion battery is successfully applied, the energy density of the lithium ion battery can be obviously improved, so that the one-time charging endurance of 1000 kilometers becomes possible. However, the charge-discharge mechanism of silicon andthe charging and discharging mechanisms of the graphite are different, and Si and Li in the electrolyte are different in the charging and discharging process + Solid Electrolyte Interface (SEI) films are continuously generated at an interface, and the formation of the irreversible SEI consumes a large amount of Li extracted from an electrolyte and a positive electrode material, so that the initial coulombic efficiency of the silicon-based negative electrode material is only 65-85%, and the great capacity loss is caused. On the other hand, the electrical conductivity and lithium ion diffusion speed of silicon are lower than those of graphite, which limits the performance of silicon under high-current and high-power conditions.
In order to solve the problems, researchers adopt processes such as lithium supplement to improve the comprehensive electrical property of the silicon-based material, and the common lithium supplement process is positive electrode lithium supplement or negative electrode lithium supplement.
CN106960945A discloses a lithium-rich silicon-based negative electrode plate, and a metal lithium foil with the diameter of about 10 μm is compounded on the negative electrode plate in a rolling manner, so that the purpose of lithium supplement of a silicon-based material is realized. CN105845894B discloses a method and a device for prelithiation of a negative electrode plate of a lithium ion battery, wherein the method comprises the steps of sequentially immersing the negative electrode plate and a metal lithium plate in an electrolyte at intervals under the condition of inert atmosphere, connecting the negative electrode plate and the metal lithium plate with a positive electrode and a negative electrode of a power supply through leads respectively, charging the negative electrode plate, and drying to obtain the prelithiated negative electrode plate. However, in the two processes, lithium powder, lithium foil or lithium strips are required to be used in the operation process, the process condition requirement is high, and the operation difficulty is high.
In order to reduce the safety hidden trouble of lithium metal in the using process, CN107819113A discloses a lithium supplement additive based on a lithium oxide core-shell structure. In the preparation process of the anode/cathode slurry, a proper amount of lithium supplement additive is added to achieve the purpose of lithium supplement of the material. But the lithium supplement additive needs to be roasted at high temperature and CO in the preparation process 2 And the obtained lithium supplement additive is sensitive to air humidity, and certain difficulty is faced in the popularization process.
Therefore, the lithium supplement additive for the electrode material, which is safe to develop, environment-friendly, convenient to store and simple and controllable in preparation process, becomes a problem to be solved urgently in the development process of the silicon-based material.
Disclosure of Invention
The invention aims to overcome the defects of complex preparation process, air-sensitive feeling and difficult storage of an electrode material lithium supplement additive in the prior art, and provides the electrode material lithium supplement additive, a preparation method and application thereof and a lithium ion battery. The lithium supplement additive for the electrode material provided by the invention is convenient to store, has no special requirements on the use working condition, and can improve the specific capacity of the material when being used in the electrode material.
In order to achieve the above object, a first aspect of the present invention provides a lithium supplement additive for an electrode material, wherein the lithium supplement additive comprises a polymer lithium salt and a carbon film coated on the surface of the polymer lithium salt.
Preferably, the polymer lithium salt has a-C (O) -OLi group on the molecular chain.
Preferably, the polymer lithium salt is selected from at least one of lithium polyacrylate, lithium polymethacrylate, lithium polymaleate, lithium polyfumarate, lithium carboxymethyl cellulose and lithium alginate.
The second aspect of the present invention provides a method for preparing a lithium supplement additive for an electrode material, comprising:
(1) Mixing a polymer lithium salt, a carbon source and a solvent;
(2) Carrying out solid-liquid separation on the materials obtained by mixing in the step (1);
(3) And carrying out heat treatment on the solid substance obtained by the solid-liquid separation.
Preferably, the carbon source is selected from at least one of homopolymeric polyacrylic acid, copolymeric polyacrylonitrile, polyvinylpyrrolidone, polyimide, polyamide, petroleum pitch, and coal pitch.
Preferably, the solvent is an organic solvent, preferably at least one selected from the group consisting of toluene, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
The third aspect of the invention provides a lithium supplement additive for the electrode material prepared by the preparation method.
The fourth aspect of the invention provides the application of the lithium supplement additive for the electrode material in a lithium ion battery.
The fifth aspect of the invention provides a lithium ion battery, which comprises an electrode material containing a lithium supplement additive, a diaphragm and an electrolyte; the lithium supplement additive is the electrode material lithium supplement additive provided by the invention.
The electrode material lithium supplement additive provided by the invention, the preparation method and the application thereof have the following advantages:
(1) The lithium supplement additive for the electrode material provided by the invention contains lithium element, and has a core-shell structure and stable properties.
(2) The lithium supplement additive for the electrode material provided by the invention does not contain elemental lithium, is convenient to store and has no special requirements on the use working conditions.
(3) The lithium supplement additive for the electrode material contains lithium species capable of generating electrochemical reaction, can compensate lithium lost in the first charge-discharge process of the electrode material, and can obviously improve the specific capacity of the material.
(4) The lithium supplement additive for the electrode material is environment-friendly, does not generate dust and the like, and does not corrode a pole piece, equipment and operators.
The electrode material lithium supplement additive provided by the invention is used in an electrode material of a lithium ion battery, and pre-lithiation treatment is not needed in the using process, so that the reversible capacity and the first coulombic efficiency of the electrode material can be greatly improved. The embodiment shows that the first coulombic efficiency of the electrode material containing the lithium supplement additive of the electrode material can reach 91%.
Drawings
FIG. 1 is a TEM photograph of a lithium supplement additive S-1 prepared in example 1, wherein A is a shell layer of a carbon film and B is a polymer lithium salt core.
FIG. 2 is a first charge-discharge curve of a silicon-carbon negative electrode containing a lithium supplement additive S-1 prepared in example 1.
Fig. 3 is a first charge-discharge curve of the silicon carbon negative electrode prepared in comparative example 1 without the lithium supplement additive.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present specification, the median diameter refers to a particle diameter corresponding to a cumulative particle size distribution percentage of 50%, and the median diameter is generally used to indicate an average particle size of the powder. In the present invention, the median particle diameter of the lithium supplement additive for the electrode material can be obtained by dynamic light scattering characterization without specific indication.
The invention provides an electrode material lithium supplement additive in a first aspect, which comprises a polymer lithium salt and a carbon film coated on the surface of the polymer lithium salt.
According to the invention, the content of each component in the lithium supplement additive is selected in a wide range, and preferably, based on the total amount of the lithium supplement additive, the content of the polymer lithium salt is 92-99 wt%, and the content of the carbon film is 1-8 wt%; more preferably, the content of the polymer lithium salt is 94-98 wt% and the content of the carbon film is 2-6 wt% based on the total amount of the lithium supplement.
According to the present invention, it is preferable that the polymer lithium salt has a-C (O) -OLi group on the molecular chain. By adopting the preferred embodiment, the improvement of the electroactive Li is more facilitated + The content of (b).
Preferably, the polymer lithium salt is selected from at least one of lithium polyacrylate, lithium polymethacrylate, lithium polymaleate, lithium polyfumarate, lithium carboxymethyl cellulose and lithium alginate.
The molecular weight of the lithium salt is selected from a wide range, and the weight average molecular weight of the lithium salt is preferably 2000-5000000, more preferably 80000-240000.
According to the invention, the selection range of the median particle size of the lithium supplement additive is wide, preferably the median particle size of the lithium supplement additive is 0.05-5 μm, such as 0.05 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, and any value in the range of any two of these values; more preferably, the lithium supplement additive has a median particle size of 0.5 to 2 μm.
The second aspect of the present invention provides a method for preparing a lithium supplement additive for an electrode material, comprising:
(1) Mixing a polymer lithium salt, a carbon source and a solvent;
(2) Carrying out solid-liquid separation on the materials obtained by mixing in the step (1);
(3) And carrying out heat treatment on the solid substance obtained by the solid-liquid separation.
According to the present invention, the selection of the polymeric lithium salt is as described above and will not be described herein.
The polymer lithium salt may be obtained commercially or may be prepared, and the present invention is not particularly limited thereto. For example, the lithium polyacrylate may be obtained by reacting polyacrylic acid with a lithium salt (preferably lithium hydroxide). The polymethacrylic acid lithium salt can be obtained by reacting polymethacrylic acid with lithium salt (preferably lithium hydroxide). The lithium polymaleate may be obtained by reacting polymaleic acid with a lithium salt, preferably lithium hydroxide. The lithium polyfumarate may be obtained by reacting polyfumarate with a lithium salt, preferably lithium hydroxide. The lithium carboxymethyl cellulose may be obtained by reacting a salt of carboxymethyl cellulose, preferably sodium carboxymethyl cellulose, with a lithium salt, preferably lithium hydroxide. The lithium alginate is obtainable by reacting a salt of alginic acid, preferably sodium alginate, with a lithium salt, preferably lithium hydroxide. The specific reaction process can be carried out according to the conventional reaction in the field, and the invention is not described in detail herein.
According to the present invention, preferably, the carbon source is selected from at least one of homopolyacrylic acid, copoly-acrylonitrile, homopoly-acrylonitrile, polyvinylpyrrolidone, polyimide, polyamide, petroleum pitch, and coal pitch. By adopting the preferred embodiment, the formation of porous carbon is facilitated, and the electrochemical performance of the prepared lithium supplement additive is further improved.
The homo-type polyacrylic acid, the co-type polyacrylonitrile, the homo-type polyacrylonitrile, the polyvinylpyrrolidone, the polyimide, the polyamide, the petroleum pitch and the coal pitch according to the present invention have meanings conventionally understood by those skilled in the art, and are commercially available.
According to the present invention, the solvent is preferably an organic solvent, preferably at least one of toluene, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
The amount of the solvent added in the present invention is selected from a wide range, for example, the slurry obtained by mixing has a solid content of 10 to 45% by weight.
According to the present invention, the amount of the added carbon source is related to the amount of the polymeric lithium salt, and preferably, the mass ratio of the polymeric lithium salt to the carbon source is 1: (0.02-0.11); more preferably, the mass ratio of the polymer lithium salt to the carbon source is 1: (0.05-0.09).
According to the present invention, preferably, the mixing of step (1) comprises: the carbon source is dissolved in the solvent and then the polymeric lithium salt is added. Further preferably, after the addition of the lithium salt of the polymer, stirring is performed. The stirring rate is not particularly limited in the present invention, and is based on the fact that uniform mixing of the polymer lithium salt, the carbon source and the solvent can be achieved.
According to a specific embodiment of the present invention, the method comprises subjecting the mixed material to solid-liquid separation after the mixing in step (1), and subjecting the solid obtained by the solid-liquid separation to the heat treatment. The separation may be by separation methods conventional in the art, such as centrifugation.
According to a specific embodiment of the present invention, the method further comprises drying the solid material before the heat treatment, preferably at a temperature of 80-150 ℃ for a time of 2-8h.
According to the present invention, preferably, the conditions of the heat treatment include: the temperature is 550-700 ℃, and the time is 0.5-2h; further preferably, the temperature is 600-650 ℃.
In the present invention, the rate of temperature rise in the heat treatment is not particularly limited, and may be, for example, 1 to 10 ℃/min. In the embodiment of the present invention, the example is given by taking 5 ℃/min as an example, and the present invention is not limited thereto.
According to a particular embodiment of the invention, the method comprises reducing the temperature of the heat-treated product obtained in step (3) (preferably to below 50 ℃, for example to room temperature of 25 ℃). The cooling may be natural cooling.
The third aspect of the invention provides a lithium supplement additive for the electrode material prepared by the preparation method.
The fourth aspect of the invention provides the use of the above-mentioned lithium supplement additive for electrode materials in lithium ion batteries. In the research process, the inventor finds that the reversible capacity and the first coulombic efficiency of the lithium battery can be improved by using the electrode material lithium supplement additive provided by the invention in the lithium ion battery.
The invention provides a lithium ion battery, which comprises an electrode material containing the lithium supplement additive, a diaphragm and electrolyte.
The lithium supplement additive provided by the invention can be used in the negative electrode material of the lithium ion battery and can also be used in the positive electrode material of the lithium ion battery.
According to the lithium ion battery provided by the invention, the electrode material is not particularly limited, and can be various anode and cathode electrode materials conventionally used in the field. The invention is exemplified by the negative electrode material being a carbon-silicon material, NCM-523, to which the invention is not limited.
According to the invention, the amount of the lithium supplement additive is selected in a wide range, and preferably, the amount of the lithium supplement additive is 3 to 15 wt% based on the total amount of the lithium supplement additive and the electrode material.
According to the present invention, preferably, the lithium ion battery is a liquid lithium ion battery, a semi-solid lithium ion battery or an all-solid lithium ion battery.
According to the lithium ion battery provided by the invention, the separator can be selected from various separators used in the lithium ion battery known to those skilled in the art, such as a polypropylene microporous membrane, a polyethylene felt, a glass fiber felt or an ultrafine glass fiber paper.
According to the lithium ion battery provided by the invention, the electrolyte can be various conventional electrolytes, such as a nonaqueous electrolyte. The nonaqueous electrolytic solution is a solution of an electrolytic lithium salt in a nonaqueous solvent, and a conventional nonaqueous electrolytic solution known to those skilled in the art can be used. For example, the electrolyte may be selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) And lithium hexafluorosilicate (LiSiF) 6 ) At least one of (1). The non-aqueous solvent may be selected from a mixed solution of a chain ester and a cyclic ester, wherein the chain ester may be at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl Methyl Carbonate (EMC), propyl methyl carbonate (MPC), and dipropyl carbonate (DPC). The cyclic acid ester may be at least one of Ethylene Carbonate (EC), propylene Carbonate (PC), and Vinylene Carbonate (VC).
The present invention will be described in detail below by way of examples. In the following examples and comparative examples, the morphology of the lithium supplement additive for electrode materials was characterized using a transmission electron microscope, specifically, a transmission electron microscope model JEM-2100, manufactured by japan electronics corporation, under test conditions: the accelerating voltage is 160KV, the sample is placed in a copper support net and then inserted into an electron microscope for observation, and the magnification of 80 ten thousand times is used for observation.
In the following examples and comparative examples, electrochemical properties of assembled lithium ion batteries were tested using the wuhan blue battery test system (CT 2001B). The test conditions included: the voltage range is 0.005V-3V, and the current range is 0.05A-2A. Each sample was assembled with 10 coin cells and the cell performance was tested at the same voltage and current and averaged.
In the following examples and comparative examples, the content of each component in the lithium supplement additive for electrode materials was calculated by measuring the loss amount of the carbon source under the heat treatment condition and the charge ratio.
In the following examples and comparative examples, petroleum pitch is commercially available from tapox under the designation PMA. Homopolymeric polyacrylonitrile is commercially available from carbofuran under the designation 226749; the copolymer polyacrylonitrile is commercially available from carbofuran under the designation 181315; polyamides are commercially available from carbofuran under the designation P688305; polyvinylpyrrolidone is commercially available from carbofuran under the designation 902615.
In the following examples and comparative examples, the silicon-carbon material was prepared by self-making and obtained by coating silicon powder with D50 of 100nm with carbon, and the reversible capacity of the material was 908 mAh-g -1 The first coulombic efficiency was 38.9%; NCM-523 is commercially available from Capacity New energy company under the designation NCM-523S700.
In the following examples and comparative examples, the room temperature is 25 ℃.
Preparation example 1
10g of polyacrylic acid with the weight average molecular weight of 240000 is added into 40g of deionized water to prepare a polyacrylic acid solution with the mass fraction of 20%. 3.4g of lithium hydroxide is weighed and added into the polyacrylic acid solution, heated and stirred at 40 ℃ until all solids are dissolved, and dried for 4 hours at 100 ℃ to obtain the lithium polyacrylate-1.
Preparation example 2
10g of polyacrylic acid with the weight average molecular weight of 200000 is added into 40g of deionized water to prepare a polyacrylic acid solution with the mass fraction of 20%. Weighing 1.2g of lithium hydroxide, adding the lithium hydroxide into the polyacrylic acid solution, heating and stirring at 40 ℃ until all solids are dissolved, and drying at 100 ℃ for 4 hours to obtain the lithium polyacrylate-2.
Preparation example 3
10g of sodium carboxymethylcellulose with the weight-average molecular weight of 120000 is added into 40g of deionized water to prepare a sodium carboxymethylcellulose solution with the mass fraction of 20%. Weighing 1.2g of lithium hydroxide, adding the lithium hydroxide into the sodium carboxymethyl cellulose solution, heating and stirring at 40 ℃ until all solids are dissolved, and drying at 100 ℃ for 4 hours to obtain the lithium carboxymethyl cellulose-1.
Preparation example 4
10g of sodium carboxymethylcellulose with the weight-average molecular weight of 120000 is added into 40g of deionized water to prepare a sodium carboxymethylcellulose solution with the mass fraction of 20%. 3.1g of lithium hydroxide is weighed and added into the sodium carboxymethyl cellulose solution, heated and stirred at 40 ℃ until all solids are dissolved, and dried for 4 hours at 100 ℃ to obtain the lithium carboxymethyl cellulose-2.
Preparation example 5
10g of sodium alginate with the weight-average molecular weight of 80000 is added into 40g of deionized water, and a sodium alginate solution with the mass fraction of 20% is prepared. Weighing 1.2g of lithium hydroxide, adding the lithium hydroxide into the sodium alginate solution, heating and stirring at 40 ℃ until all solids are dissolved, and drying at 100 ℃ for 4h to obtain the lithium alginate-1.
Preparation example 6
10g of sodium alginate with the weight-average molecular weight of 80000 is added into 40g of deionized water, and a sodium alginate solution with the mass fraction of 20% is prepared. 3.2g of lithium carbonate is weighed and added into the sodium alginate solution, heated and stirred at the temperature of 40 ℃ until all solids are dissolved completely, and dried for 4 hours at the temperature of 100 ℃ to obtain the lithium alginate-2.
Preparation example 7
10g of polyacrylic acid with the weight average molecular weight of 240000 is added into 40g of deionized water to prepare a polyacrylic acid solution with the mass fraction of 20%. 3.2g of lithium carbonate is weighed and added into the polyacrylic acid solution, heated and stirred at the temperature of 40 ℃ until all solids are dissolved completely, and dried for 4 hours at the temperature of 100 ℃ to obtain the lithium polyacrylate-3.
Preparation example 8
10g of polymethacrylic acid with the weight-average molecular weight of 240000 is added into 40g of deionized water to prepare a polymethacrylic acid solution with the mass fraction of 20%. 3.2g of lithium carbonate is weighed and added into the polymethacrylic acid solution, heated and stirred at 40 ℃ until all solids are dissolved, and dried for 4 hours at 100 ℃ to obtain the polymethacrylic acid lithium-1.
Preparation example 9
10g of polymaleic acid with the weight-average molecular weight of 240000 is added into 40g of deionized water to prepare a polymaleic acid solution with the mass fraction of 20%. 3.2g of lithium carbonate is weighed and added into the polymaleic acid solution, heated and stirred at 40 ℃ until all solids are dissolved, and dried for 4 hours at 100 ℃ to obtain the polymaleic acid lithium-1.
Preparation example 10
10g of polyfumaric acid with the weight-average molecular weight of 240000 is added into 40g of deionized water to prepare a polyfumaric acid solution with the mass fraction of 20%. 3.2g of lithium carbonate is weighed and added into the poly fumaric acid solution, heated and stirred at the temperature of 40 ℃ until all solids are dissolved, and dried for 4 hours at the temperature of 100 ℃ to obtain the poly lithium fumarate-1.
Example 1
(1) Dissolving 5g of petroleum asphalt in 200mL of toluene, adding 65g of lithium polyacrylate-1, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solids, and drying at 100 ℃ for 4h to obtain a precursor of the lithium supplement additive;
(3) And (3) putting 2g of the precursor into a tubular furnace, heating to 600 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-1. The median particle size of the lithium supplement additive S-1 and the contents of the components are shown in Table 1.
A silicon carbon material (mass content: 10%) containing the lithium supplement additive obtained in example 1, and metallic lithium pieces were used as a positive electrode and a negative electrode, respectively, and 1mol/L LiPF was used 6 The solution (ethylene carbonate and diethyl carbonate are mixed in a volume ratio of 3:7 as a solvent) is used as an electrolyte, a polypropylene microporous membrane is used as a diaphragm, and the diaphragm is assembled into a CR2016 coin cell, thereby representing the electrical properties of the electrode material added with the lithium supplement additive S-1 in example 1.
FIG. 1 is a TEM photograph of the lithium supplement additive. As can be seen from the figure, the surface of the polymer lithium salt A is uniformly wrapped with the carbon film B, and the existence of the carbon film improves the stability of the lithium supplement additive, so that the lithium supplement additive can stably exist at room temperature.
FIG. 2 shows the first charging and discharging curves (test voltage range 0.05-3V, current 50 mA) of a button cell based on the material described in example 1. As shown, the material of example 1 has a reversible charge capacity of 3000mAh g -1 The first coulombic efficiency was 86.9%.
Example 2
(1) Dissolving 5g of homopolymerized polyacrylonitrile in 40mL of N, N-dimethylformamide, adding 50g of lithium polyacrylate-1, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solid, and drying for 4h at 100 ℃ to obtain a precursor of the lithium supplement additive;
(3) And (3) putting 2g of the precursor into a tube furnace, heating to 650 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-2. The median particle size of the lithium supplement additive S-2 and the contents of the components are shown in Table 1.
TEM photographs of the lithium supplement additive S-2 were similar to those of FIG. 1.
A silicon carbon material (mass content: 10%) containing the lithium supplement additive obtained in example 2, and metallic lithium pieces were used as a positive electrode and a negative electrode, respectively, and 1mol/L LiPF was used 6 The solution (ethylene carbonate and diethyl carbonate mixed in a volume ratio of 3:7 as a solvent) was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and a CR2016 coin cell was assembled, and the electrical properties of the electrode material with the lithium supplement additive S-2 added thereto were measured as described in example 1, and the results are shown in table 1.
Example 3
(1) Dissolving 5g of polyamide in 40mL of N, N-dimethylformamide, adding 86g of lithium polyacrylate-1, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solids, and drying at 100 ℃ for 4h to obtain a precursor of the lithium supplement additive;
(3) And (3) putting 2g of the precursor into a tube furnace, heating to 650 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-3. The median particle size of the lithium supplement additive S-3 and the contents of the components are shown in Table 1.
TEM photographs of the lithium supplement additive S-3 were similar to those of FIG. 1.
The silicon-carbon material (mass content: 10%) containing the lithium supplement additive obtained in example 3, and the metallic lithium pieces were used as a positive electrode and a negative electrode, respectively, and 1mol/L LiPF was used 6 The solution (ethylene carbonate and diethyl carbonate mixed in a volume ratio of 3:7 as a solvent) was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and a CR2016 coin cell was assembled by the method described in example 1 for the electrode material to which the lithium supplement additive S-3 was addedThe electrical properties of (A) were tested and the results are shown in Table 1.
Example 4
(1) Dissolving 5g of polyvinylpyrrolidone in 40mL of N-methyl pyrrolidone, adding 62g of lithium polyacrylate-2, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solid, and drying for 4h at 100 ℃ to obtain a precursor of the lithium supplement additive;
(3) And (3) taking 2g of the precursor, placing the precursor in a tube furnace, heating to 650 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-4. The median particle size of the lithium supplement additive S-4 and the contents of the components are listed in Table 1.
TEM photographs of the lithium supplement additive S-4 were similar to those of FIG. 1.
A silicon carbon material (mass content: 10%) containing the lithium supplement additive obtained in example 4 and metallic lithium pieces were used as a positive electrode and a negative electrode, respectively, and 1mol/L LiPF was used 6 The solution (ethylene carbonate and diethyl carbonate mixed in a volume ratio of 3:7 as a solvent) was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and a CR2016 coin cell was assembled, and the electrical properties of the electrode material with the lithium supplement additive S-4 added thereto were tested as described in example 1, and the results are shown in table 1.
Example 5
(1) Dissolving 5g of polyvinylpyrrolidone in 40mL of N-methyl pyrrolidone, adding 75g of lithium carboxymethyl cellulose-1, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solids, and drying at 100 ℃ for 4h to obtain a precursor of the lithium supplement additive;
(3) And (3) putting 2g of the precursor into a tube furnace, heating to 650 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-5. The median particle size of the lithium supplement additive S-5 and the contents of the components are shown in Table 1.
TEM photographs of the lithium supplement additive S-5 are similar to those of FIG. 1.
Respectively compriseThe silicon-carbon material (10% by mass) of the lithium supplement additive obtained in example 5, the metal lithium pieces used as the positive electrode and the negative electrode, and 1mol/L LiPF 6 The solution (ethylene carbonate and diethyl carbonate mixed in a volume ratio of 3:7 as a solvent) was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and a CR2016 coin cell was assembled, and the electrical properties of the electrode material with the lithium supplement additive S-5 added thereto were measured as described in example 1, and the results are shown in table 1.
Example 6
(1) Dissolving 5g of copolymerized polyacrylonitrile in 40mL of N-methyl pyrrolidone, adding 83g of lithium carboxymethyl cellulose-2, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solids, and drying at 100 ℃ for 4h to obtain a precursor of the lithium supplement additive;
(3) And (3) putting 2g of the precursor into a tube furnace, heating to 650 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-6. The median particle size of the lithium supplement additive S-6 and the contents of the components are shown in Table 1.
TEM photographs of lithium supplement additive S-6 are similar to FIG. 1.
A silicon carbon material (mass content: 10%) containing the lithium supplement additive obtained in example 6, metallic lithium pieces as a positive electrode and a negative electrode, and 1mol/L LiPF were used 6 The solution (ethylene carbonate and diethyl carbonate mixed in a volume ratio of 3:7 as a solvent) was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and a CR2016 coin cell was assembled, and the electrical properties of the electrode material with the lithium supplement additive S-6 added thereto were tested as described in example 1, and the results are shown in table 1.
Example 7
(1) Dissolving 5g of petroleum asphalt in 40mL of N-methyl pyrrolidone, adding 48g of lithium carboxymethyl cellulose-1, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solid, and drying for 4h at 100 ℃ to obtain a precursor of the lithium supplement additive;
(3) And (3) putting 2g of the precursor into a tube furnace, heating to 650 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-7. The median particle size of the lithium supplement additive S-7 and the contents of the components are listed in Table 1.
TEM photographs of the lithium supplement additive S-7 are similar to those of FIG. 1.
A silicon carbon material (mass content: 10%) containing the lithium supplement additive obtained in example 7 and metallic lithium pieces were used as a positive electrode and a negative electrode, respectively, and 1mol/L LiPF was used 6 The solution (ethylene carbonate and diethyl carbonate mixed in a volume ratio of 3:7 as a solvent) was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and a CR2016 coin cell was assembled, and the electrical properties of the electrode material with the lithium supplement additive S-7 added thereto were tested as described in example 1, and the results are shown in table 1.
Example 8
(1) Taking 5g of polyvinylpyrrolidone, dissolving the polyvinylpyrrolidone in 40mL of N-methylpyrrolidone, adding 56g of lithium alginate-1, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solids, and drying at 100 ℃ for 4h to obtain a precursor of the lithium supplement additive;
(3) And (3) putting 2g of the precursor into a tube furnace, heating to 650 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-8. The median particle size of the lithium supplement additive S-8 and the contents of the components are shown in Table 1.
TEM photographs of the lithium supplement additive S-8 are similar to those of FIG. 1.
A silicon carbon material (mass content: 10%) containing the lithium supplement additive obtained in example 8 and metallic lithium pieces were used as a positive electrode and a negative electrode, respectively, and 1mol/L LiPF was used 6 The solution (ethylene carbonate and diethyl carbonate mixed in a volume ratio of 3:7 as a solvent) was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and a CR2016 coin cell was assembled, and the electrical properties of the electrode material with the lithium supplement additive S-8 added thereto were tested as described in example 1, and the results are shown in table 1.
Example 9
(1) Dissolving 5g of petroleum asphalt in 40mL of N-methyl pyrrolidone, adding 65g of lithium alginate-2, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solid, and drying for 4h at 100 ℃ to obtain a precursor of the lithium supplement additive;
(3) And (3) taking 2g of the precursor, placing the precursor in a tube furnace, heating to 650 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-9. The median particle size of the lithium supplement additive S-9 and the contents of the components are listed in Table 1.
TEM photographs of the lithium supplement additive S-2 were similar to those of FIG. 1.
A silicon carbon material (mass content: 10%) containing the lithium supplement additive obtained in example 2, and metallic lithium pieces were used as a positive electrode and a negative electrode, respectively, and 1mol/L LiPF was used 6 The solution (ethylene carbonate and diethyl carbonate mixed in a volume ratio of 3:7 as a solvent) was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and a CR2016 coin cell was assembled, and the electrical properties of the electrode material with the lithium supplement additive S-9 added thereto were tested as described in example 1, and the results are shown in table 1.
Example 10
(1) Dissolving 5g of copolymerization polyacrylonitrile in 40mL of N-methyl pyrrolidone, adding 60g of lithium polyacrylate-3, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solids, and drying at 100 ℃ for 4h to obtain a precursor of the lithium supplement additive;
(3) And (3) putting 2g of the precursor into a tube furnace, heating to 650 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-10. The median particle size of the lithium supplement additive S-10 and the contents of the components are shown in Table 1.
TEM photographs of lithium supplement additive S-10 are similar to FIG. 1.
NCM-523 (10% by mass) containing the lithium supplement additive obtained in example 10, and lithium metal sheets were used as a positive electrode and a negative electrode, respectively, and 1mol/L LiPF was used 6 Solution (carbonic acid)Ethylene ester and diethyl carbonate in a ratio of 3:7 volume ratio as solvent) as an electrolyte, a polypropylene microporous membrane as a diaphragm, and assembled into a CR2016 coin cell, the electrical properties of the electrode material with the lithium supplement additive S-10 added were tested as described in example 1, and the results are listed in table 1.
Example 11
(1) Dissolving 5g of petroleum asphalt in 200mL of toluene, adding 65g of lithium polymethacrylate-1, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solids, and drying at 100 ℃ for 4h to obtain a precursor of the lithium supplement additive;
(3) And (3) putting 2g of the precursor into a tube furnace, heating to 620 ℃ at the speed of 5 ℃/min, preserving the temperature for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-11. The median particle size of the lithium supplement additive S-11 and the contents of the components are shown in Table 1.
TEM photographs of lithium supplement additive S-11 are similar to FIG. 1.
NCM-523 (10% by mass) containing the lithium supplement additive obtained in example 11, and lithium metal sheets were used as a positive electrode and a negative electrode, respectively, and 1mol/L LiPF was used 6 The solution (ethylene carbonate and diethyl carbonate mixed in a volume ratio of 3:7 as a solvent) was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and a CR2016 coin cell was assembled, and the electrical properties of the electrode material with the lithium supplement additive S-11 added thereto were tested as described in example 1, and the results are shown in table 1.
Example 12
(1) Dissolving 5g of petroleum asphalt in 200mL of toluene, adding 65g of polymaleic acid lithium-1, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solids, and drying at 100 ℃ for 4h to obtain a precursor of the lithium supplement additive;
(3) And (3) putting 2g of the precursor into a tube furnace, heating to 680 ℃ at the speed of 5 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-12. The median particle size of the lithium supplement additive S-12 and the content of each component are listed in Table 1.
TEM photographs of the lithium supplement additive S-12 are similar to those of FIG. 1.
NCM-523 (10% by mass) containing the lithium supplement additive obtained in example 12, and lithium metal sheets were used as a positive electrode and a negative electrode, respectively, and 1mol/L LiPF was used 6 The solution (ethylene carbonate and diethyl carbonate mixed in a volume ratio of 3:7 as a solvent) was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and a CR2016 coin cell was assembled, and the electrical properties of the electrode material with the lithium supplement additive S-12 added thereto were tested as described in example 1, and the results are shown in table 1.
Example 13
(1) Dissolving 5g of petroleum asphalt in 200mL of toluene, adding 65g of lithium polyfumarate-1, and stirring for 1h;
(2) After stirring, transferring the slurry into a 50mL centrifugal tube, centrifuging for 5min at the rotating speed of 5000rpm, collecting lower-layer solids, and drying at 100 ℃ for 4h to obtain a precursor of the lithium supplement additive;
(3) And (3) putting 2g of the precursor into a tube furnace, heating to 600 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the lithium supplement additive S-13. The median particle size of the lithium supplement additive S-13 and the contents of the components are listed in Table 1.
TEM photographs of the lithium supplement additive S-13 are similar to those of FIG. 1.
NCM-523 (10% by mass) containing the lithium supplement additive obtained in example 13, and lithium metal sheets as a positive electrode and a negative electrode were used, respectively, and LiPF (1 mol/L) was used 6 The electrical properties of the electrode material with the lithium supplement additive S-13 added thereto were tested as described in example 1 using a solution (ethylene carbonate and diethyl carbonate mixed in a volume ratio of 3:7 as a solvent) as an electrolyte and a polypropylene microporous membrane as a separator to assemble a CR2016 coin cell, and the results are listed in table 1.
Comparative example 1
Respectively using silicon carbon material and metal lithium sheet as positive electrode and negative electrode, and using 1mol/L LiPF 6 The solution (the mixture of ethylene carbonate and diethyl carbonate in the volume ratio of 3:7 is used as solvent) is used as electrolyte, and the polypropylene microporous membrane is used asAnd the diaphragm is assembled into a CR2016 button cell, and the electrical property of the silicon-carbon material is characterized.
FIG. 3 shows the first charge-discharge curve (test voltage range 0.05-3V, current 50 mA) of a coin cell based on the material described in comparative example 1. As shown, the material of comparative example 1 had a reversible charge capacity of 908mAh g -1 The first coulombic efficiency was 38.9%.
TABLE 1
Figure BDA0002226416000000191
It can be seen from the results in table 1 that the reversible charge capacity and the first coulombic efficiency of the electrode material can be improved by using the lithium supplement additive provided by the present invention in the electrode material.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (17)

1. The lithium supplement additive for the silicon-carbon negative electrode material is characterized by comprising a polymer lithium salt and a carbon film coated on the surface of the polymer lithium salt;
based on the total amount of the lithium supplement additive, the content of the polymer lithium salt is 92-99 wt%; the content of the carbon film is 1-8 wt%;
the weight average molecular weight of the polymer lithium salt is 80000-240000;
the polymer lithium salt has a-C (O) -OLi group on the molecular chain.
2. The lithium supplement additive of claim 1, wherein the polymeric lithium salt is present in an amount of 94-98 wt%, based on the total amount of lithium supplement additive; the content of the carbon film is 2-6 wt%.
3. The lithium replenishment additive of claim 1, wherein the polymeric lithium salt is selected from at least one of lithium polyacrylate, lithium polymethacrylate, lithium polymaleate, lithium polyfumarate, lithium carboxymethyl cellulose, and lithium alginate.
4. The lithium supplement additive according to any one of claims 1 to 3, wherein the lithium supplement additive has a median particle size of 0.05 to 5 μm.
5. The lithium supplement additive of claim 4, wherein the lithium supplement additive has a median particle size of 0.5-2 μm.
6. A preparation method of a lithium supplement additive for a silicon-carbon negative electrode material comprises the following steps:
(1) Mixing a polymer lithium salt, a carbon source and a solvent;
(2) Carrying out solid-liquid separation on the materials obtained by mixing in the step (1);
(3) Carrying out heat treatment on the solid matter obtained by the solid-liquid separation to obtain a lithium supplement additive, wherein the lithium supplement additive comprises a polymer lithium salt and a carbon film coated on the surface of the polymer lithium salt;
the weight average molecular weight of the polymer lithium salt is 80000-240000;
the mass ratio of the polymer lithium salt to the carbon source is 1: (0.02-0.11);
the polymer lithium salt has a-C (O) -OLi group on the molecular chain.
7. The production method according to claim 6, wherein the polymer lithium salt is selected from at least one of lithium polyacrylate, lithium polymethacrylate, lithium polymaleate, lithium polyfumarate, lithium carboxymethyl cellulose, and lithium alginate.
8. The production method according to claim 6, wherein the carbon source is at least one selected from the group consisting of homopolyacrylic acid, copoly polyacrylonitrile, polyvinylpyrrolidone, polyimide, polyamide, petroleum pitch, and coal pitch.
9. The production method according to claim 6, wherein the solvent is an organic solvent.
10. The production method according to claim 9, wherein the solvent is at least one selected from the group consisting of toluene, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
11. The production method according to claim 6, wherein the mixing of step (1) includes: the carbon source is dissolved in the solvent and then the polymeric lithium salt is added.
12. The preparation method according to claim 6, wherein the amount mass ratio of the polymer lithium salt to the carbon source is 1: (0.05-0.09).
13. The production method according to any one of claims 6 to 12, wherein the conditions of the heat treatment include: the temperature is 550-700 deg.C, and the time is 0.5-2h.
14. The lithium supplement additive for the silicon-carbon negative electrode material prepared by the preparation method of any one of claims 6 to 13.
15. Use of the silicon carbon negative electrode material lithium supplement additive of any one of claims 1-5 and 14 in a lithium ion battery.
16. A lithium ion battery comprises a silicon-carbon negative electrode material containing a lithium supplement additive, a diaphragm and electrolyte; the lithium supplement additive is the silicon-carbon negative electrode material lithium supplement additive of any one of claims 1-5 and 14.
17. The lithium ion battery of claim 16, wherein the lithium ion battery is a liquid lithium ion battery, a semi-solid lithium ion battery, or an all-solid lithium ion battery.
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