CN113140705A - Secondary battery cathode, preparation method thereof and secondary battery - Google Patents

Secondary battery cathode, preparation method thereof and secondary battery Download PDF

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CN113140705A
CN113140705A CN202010048366.1A CN202010048366A CN113140705A CN 113140705 A CN113140705 A CN 113140705A CN 202010048366 A CN202010048366 A CN 202010048366A CN 113140705 A CN113140705 A CN 113140705A
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negative electrode
secondary battery
tin
pore
graphitized carbon
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胡倩倩
洪晔
吴春宇
长世勇
董海勇
胡志鹏
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Guangzhou Automobile Group Co Ltd
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H—ELECTRICITY
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    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention is applied to the field of secondary batteries, and provides a secondary battery cathode aiming at the defect that the cycle performance and the multiplying power performance are poor due to pole piece pulverization caused by volume expansion in the charging and discharging processes of a tin-based material serving as a cathode active material in the prior art. Compared with the prior art, the cathode active substance has a three-dimensional structure and abundant holes and pore size distribution, provides a space for the particle expansion of the tin-based material, can effectively prevent the agglomeration of small particles in the charging and discharging processes, has a larger specific surface area, is beneficial to the infiltration of electrolyte, is beneficial to the diffusion speed of lithium/sodium/potassium ions, and integrally improves the cycle performance, the better rate charging and discharging electrical properties and the like.

Description

Secondary battery cathode, preparation method thereof and secondary battery
Technical Field
The invention is applied to the field of secondary batteries such as lithium ion, potassium ion or sodium ion, and particularly relates to a secondary battery cathode and a preparation method thereof.
Background
With the development of science and technology, the requirements of portable equipment and new energy electric vehicles on the energy density of energy storage devices are higher and higher. Lithium batteries are widely used due to their high energy density, no memory effect and excellent cycling performance. However, the theoretical gram capacity of the graphite which is generally used as the negative electrode of the lithium battery is only 372mAh/g, so that the increase of the energy density of the lithium battery is limited. Tin-based materials (tin disulfide, tin monosulfide, etc.) are of interest because of their higher theoretical gram capacity than graphite. But it has certain problems in itself: the huge volume expansion in the charge-discharge process leads to pole piece pulverization in the circulation process, and meanwhile, larger particles influence the diffusion speed of lithium ions and have certain influence on the multiplying power performance of the battery.
The existing tin sulfide/carbon nanotube composite nanometer negative electrode material adopts the carbon nanotube as a base material to load tin disulfide, the carbon nanotube has a smaller specific surface and does not have abundant pore structures, the volume expansion of the carbon nanotube is not easy to relieve, and in addition, the calcining temperature of the carbon nanotube is 600 ℃, the energy consumption is higher, and the full utilization of resources is not easy.
According to the existing composite material with the hollow graphene spheres loaded with the nano tin disulfide, the hollow graphene spheres with submicron sizes are used as carriers, nano tin disulfide particles are loaded on the inner wall and the outer wall of each graphene hollow sphere, and the size of the tin disulfide particles growing on the surfaces of the hollow graphene spheres is 10-40 nm. The composite material carrier is a hollow graphene ball with submicron size, but the pore structure is single and not abundant enough.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the secondary battery negative electrode is provided aiming at the defect that tin-based materials as negative electrode active materials cause pole piece pulverization due to volume expansion in the charging and discharging processes and further cause poor cycle performance and rate performance in the prior art, the negative electrode comprises the negative electrode active materials with a new bearing structure, the negative electrode active materials have a three-dimensional structure and rich holes and pore size distribution, space is provided for particle expansion of the nanoscale tin-based materials, small particles can be effectively prevented from agglomerating in the charging and discharging processes, and then the cycle performance and the rate charging and discharging performance of the battery are effectively improved.
In order to solve the technical problems, the invention provides a secondary battery negative electrode, which comprises a current collector and a negative electrode material coated on the current collector, wherein the negative electrode material comprises a negative electrode active substance, a conductive agent and a binder, the negative electrode active substance comprises a graphitized carbon material with an open pore three-dimensional structure and multi-level pore diameter distribution, and the surface of the graphitized carbon material is loaded with a tin-based material of nano-scale particles.
Optionally, the tin-based material includes tin disulfide nanoparticles, and the average particle size of the tin disulfide nanoparticles is 2-5 nm.
Optionally, the tin-based material comprises tin sulfide nanorods, and the average length of the tin sulfide nanorods is 50-200nm, and the average diameter of the tin sulfide nanorods is 10-50 nm.
Optionally, the graphitized carbon material comprises a microporous structure with a pore diameter of less than 2nm, a mesoporous structure with a pore diameter of 2-50nm, a nanoscale macropore with a pore diameter of more than 50nm, and a micrometer-scale macroscopic pore multi-level open pore self-supporting three-dimensional structure.
Optionally, the weight ratio of the negative electrode active material is 55-95%, the weight ratio of the conductive agent is 2-15%, and the weight ratio of the binder is 3-30%.
Optionally, the weight ratio of the negative electrode active material is preferably 60% to 80%, and the total weight ratio of the conductive agent and the binder is 20% to 40%.
In order to solve the technical problem, the invention also provides a preparation method of the secondary battery cathode, which comprises the following steps:
coating a negative electrode material including a negative electrode active material, a conductive agent and a binder on a current collector, wherein the negative electrode active material is prepared by the steps of:
(1) dispersing the graphitized carbon material with an open pore three-dimensional structure with multi-level pore size distribution in a strong acid or strong alkali solution, carrying out hydrothermal reaction, filtering a reaction product, washing the reaction product to be neutral by using deionized water, and drying the reaction product to obtain a functionalized graphitized carbon material;
(2) dispersing the functional graphitized carbon material in a solvent, stirring, adding a tin source and a sulfur source, carrying out hydrothermal reaction, filtering and cleaning a reaction product, and drying to obtain the negative active material.
Optionally, the method for preparing the negative active material further comprises the step (3): and (3) carrying out heat treatment on the negative electrode active material obtained in the step (2) in an inert atmosphere, wherein the heat treatment temperature is 400-500 ℃, and the time is 1-3 h.
Optionally, the graphitized carbon material with an open pore three-dimensional structure having a plurality of layers of pore size distributions in step (1) is prepared by the following steps:
(a) mixing the large-mesh resin with a metal ion salt solution, stirring, drying, and crushing to obtain a resin capable of adsorbing metal ions; (b) preparing a transitional die cavity filler aqueous solution and a pore-expanding agent solution, respectively adding the resin for adsorbing the metal ions into the transitional die cavity filler solution and the pore-expanding agent solution, mixing the solutions, stirring, drying, and crushing again; (c) carrying out heat treatment on the product obtained in the step (b) in an inert gas atmosphere; (d) and (c) carrying out acid washing, filtering and drying on the product obtained in the step (c) to obtain the three-dimensional structure graphitized carbon material with multi-level open pores with pore diameter distribution.
Optionally, the strong base in the step (1) is sodium hydroxide or potassium hydroxide, the strong acid is sulfuric acid or nitric acid, the concentration is 2-6mol/L, the hydrothermal reaction temperature is 100-200 ℃, and the time is 2-6 h.
Optionally, the solvent in the step (2) is selected from ethylene glycol, ethanol, polyethylene glycol or water, the stirring is ultrasonic stirring, the stirring time is 0.5-2h, the used tin source is at least one of tin chloride and stannous chloride, the sulfur source is at least one of thiourea, sodium sulfide and sodium thiosulfate, the hydrothermal reaction temperature is 100-220 ℃, and the hydrothermal reaction time is 10-24 h. Further, the solvent is preferably ethylene glycol, ethanol or polyethylene glycol, and the hydrothermal reaction temperature is preferably 160-220 ℃, and the time is preferably 20-24 h.
The invention also provides a secondary battery, which comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that the negative electrode comprises at least one of the negative electrode active materials.
Compared with the prior art, the cathode active material adopted by the cathode of the secondary battery has nano-grade tin-based material particles loaded on the hierarchical pore graphitized carbon, the cathode active material has a three-dimensional structure, and abundant holes and pore size distribution, provide space for the particle expansion of tin-based materials (such as tin monosulfide, tin disulfide and the like), and the complex holes can effectively prevent the agglomeration of small particles in the charging and discharging process, and can play a role in embedding a part of nano rods and irregular nano particles, thereby slowing down the pulverization process of tin-based material particles caused by expansion, and the porous graphitized carbon has larger specific surface area, is beneficial to the infiltration of electrolyte, further facilitating the diffusion speed of lithium/sodium/potassium ions, and integrally improving the cycle performance, multiplying power charge and discharge performance and the like.
Drawings
FIG. 1 is a HPGC/SnS prepared in example 1 of the invention2XRD pattern of tin disulfide;
FIG. 2 is a HPGC/SnS prepared in example 1 of the present invention2TEM pictures of 50nm size units;
FIG. 3 is HPGC/SnS prepared in example 1 of the present invention2TEM pictures of 5nm size units;
FIG. 4 is an XRD pattern of tin monosulfide for HPGC/SnS prepared in accordance with example 2 of the present invention;
FIG. 5 is a TEM picture of 50nm size unit of HPGC/SnS prepared in example 2 of the present invention;
figure 6 is an SEM image of tin disulfide prepared for comparative example 1;
FIG. 7 is an SEM image of the tin monosulfide prepared in comparative example 2;
FIG. 8 is a graph comparing the cycling performance of examples of the present invention and comparative examples in a lithium battery system;
FIG. 9 is a graph comparing rate performance of inventive and comparative examples in a lithium battery system;
FIG. 10 is an SEM image of a three-dimensional structure graphitized carbon material (HPGC) prepared by an example of the present invention;
FIG. 11 is a TEM image of a graphitized carbon material with a three-dimensional structure (HPGC) prepared by an example of the present invention;
FIG. 12 is a BET pore size distribution plot of a three-dimensional structure graphitized carbon material (HPGC) prepared by an example of the present invention;
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a secondary battery negative electrode which comprises a current collector and a negative electrode material coated on the current collector, wherein the negative electrode material comprises a negative electrode active substance, a conductive agent and a binder, the negative electrode active substance comprises a graphitized carbon material with an open pore three-dimensional structure and multi-level pore diameter distribution, and the surface of the graphitized carbon material is loaded with a tin-based material of nano-scale particles. The surface of the graphitized carbon material comprises an outer surface of the graphitized carbon material and/or an inner surface of the multi-layered open pores. As one embodiment of the invention, the graphitized carbon material comprises a multilayer open pore self-supporting three-dimensional structure with micropores with the pore diameter of less than 2nm, mesopores with the pore diameter of 2-50nm, nano-scale macropores with the pore diameter of more than 50nm and micron-scale macroscopic pores. The electrolyte solution provides abundant space for particle expansion of tin-based materials (such as tin sulfide, tin disulfide and the like), can effectively prevent agglomeration of small particles in the charging and discharging process, has a large specific surface area, is favorable for infiltration of the electrolyte solution, and improves cycle performance, multiplying power charging and discharging electrical properties and the like.
As one embodiment of the present invention, the tin-based material includes tin disulfide nanoparticles having an average particle diameter of 2 to 5 nm.
As one embodiment of the invention, the tin-based material comprises tin sulfide nanorods, and the average length of the tin sulfide nanorods is 50-200nm, and the average diameter of the tin sulfide nanorods is 10-50 nm. The preferred embodiment takes tin monosulfide as the tin-based material, and has higher specific energy than tin disulfide, and more excellent cycle performance and rate charge and discharge performance. In addition, potassium ion batteries and sodium ion batteries are also one of the directions of future energy storage devices, and tin sulfide is used as a negative electrode active component, so that the potassium ion batteries and the sodium ion batteries have certain advantages because the specific energy of the tin sulfide is higher than that of the existing pure carbon materials.
In one embodiment of the present invention, the negative electrode active material is 55 to 95 wt%, the conductive agent is 2 to 15 wt%, and the binder is 3 to 30 wt%. More preferably, the weight ratio of the negative electrode active material is 60% to 80%, and the total weight ratio of the conductive agent and the binder is 20% to 40%. Within the weight ratio range, the multiplying power charge-discharge performance and the cycle performance are improved on the basis of fully exerting the capacity of the lithium ion battery.
The conductive agent is not particularly limited, and may be a negative electrode conductive agent conventional in the art or commercially available, such as carbon black, conductive graphite, carbon fiber, carbon nanotube, graphene, and the like; the binder is not particularly limited, and a conventional negative electrode binder in the art or commercially available, such as polyvinylidene fluoride (PVDF), aqueous carboxymethyl cellulose (CMC), etc.; the current collector is not particularly limited, and a negative electrode current collector, such as a copper foil, which is conventional in the art, may be used.
As one embodiment of the present invention, the present invention provides a method for preparing a negative electrode of a secondary battery, comprising the steps of: coating a negative electrode material including a negative electrode active material, a conductive agent and a binder on a current collector, wherein the negative electrode active material is prepared by the steps of: (1) dispersing the graphitized carbon material with an open pore three-dimensional structure with multi-level pore size distribution in a strong acid or strong alkali solution, carrying out hydrothermal reaction, filtering a reaction product, washing the reaction product to be neutral by using deionized water, and drying the reaction product to obtain a functionalized graphitized carbon material; (2) dispersing the functional graphitized carbon material in a solvent, stirring, adding a tin source and a sulfur source, carrying out hydrothermal reaction, filtering and cleaning a reaction product, and drying to obtain the negative active material.
As one specific embodiment of the invention, the strong base in the step (1) is sodium hydroxide or potassium hydroxide, the strong acid is sulfuric acid or nitric acid, the concentration is 2-6mol/L, the hydrothermal reaction temperature is 100-200 ℃, and the time is 2-6h, so that the degree of functionalization of the hierarchical porous carbon material is high.
As one embodiment of the present invention, the solvent in step (2) is selected from ethylene glycol, ethanol, polyethylene glycol or water, the stirring is ultrasonic stirring, the stirring time is 0.5 to 2 hours, the tin source used is at least one of tin chloride and stannous chloride, the sulfur source is at least one of thiourea, sodium sulfide and sodium thiosulfate, and the molar ratio of the tin source to the sulfur source is 1: 2-4, the hydrothermal reaction temperature is 100-220 ℃, and the time is 10-24 h. Further, the solvent is preferably an organic solvent such as ethylene glycol, ethanol or polyethylene glycol, the hydrothermal reaction temperature is preferably 160-220 ℃, and the time is preferably 20-24 h. Therefore, the sulfur source, the tin source and the hierarchical porous carbon can react more fully, and the reaction product is tin disulfide. Through the step (2), the nano-scale tin disulfide can be loaded on the surface of the graphitized carbon material with the open pore three-dimensional structure with multi-level pore size distribution.
As one embodiment of the present invention, the method for preparing the anode active material further comprises the step (3): and (3) carrying out heat treatment on the negative electrode active material obtained in the step (2) in an inert atmosphere, wherein the heat treatment temperature is 400-500 ℃, and the time is 1-3 h. And (3) converting the tin disulfide into tin sulfide, wherein the inert atmosphere can adopt a conventional means such as nitrogen, the heat treatment temperature is not lower than 400 and not higher than 500 ℃, the heat preservation time is not lower than 1h and not higher than 3h, the reaction is insufficient when the temperature is too low, the too high tin sulfide is easy to agglomerate, the heat preservation time is too short and is not beneficial to complete conversion, and the tin sulfide is easy to agglomerate when the temperature is too long.
The preparation method of the graphitized carbon material with the three-dimensional structure of the open pores with the multi-level pore size distribution in the step (1) can adopt resin as a raw material, metal ion salts such as cobalt salt or nickel salt as a catalytic template, and alkali compounds as a pore-forming agent, and prepare the graphitized hierarchical pore carbon material with the high specific surface area by a melt cracking method.
As one embodiment of the present invention, the graphitized carbon material having an open pore three-dimensional structure with a plurality of layers of pore size distribution in step (1) is prepared by the following steps:
(a) mixing the large-mesh resin with a metal ion salt solution, stirring, drying, and crushing to obtain a resin capable of adsorbing metal ions; (b) preparing a transitional die cavity filler aqueous solution and a pore-expanding agent solution, respectively adding the resin for adsorbing the metal ions into the transitional die cavity filler solution and the pore-expanding agent solution, mixing the solutions, stirring, drying, and crushing again; (c) carrying out heat treatment on the product obtained in the step (b) in an inert gas atmosphere; (d) and (c) carrying out acid washing, filtering and drying on the product obtained in the step (c) to obtain the three-dimensional structure graphitized carbon material with multi-level open pores with pore diameter distribution.
Wherein the macroreticular resin is used as a carbon source and the self-template is resin with a porous and macroreticular structure. The large mesh resin comprises one or a mixture of two or more of macroporous ion exchange resin, macroporous adsorption resin and an intermediate thereof.
Wherein the concentration of the metal ion salt in the metal ion salt aqueous solution is 0.1-0.5 mol/L; the dosage ratio of the metal ion salt to the resin is 0.04mol-3.2 mol: 1 kg; the metal ion salt is selected from one or more of ferric chloride, ammonium ferrous sulfate, ferric sulfate, potassium ferricyanide, potassium ferrocyanide, sodium nitrosoferricyanide, ferric nitrate, ferric citrate, ferrous sulfide, ferric oxalate, cobalt chloride, cobalt sulfate, cobalt nitrate, sodium cobalt nitrite, cobalt acetate, potassium cobalt nitrite, nickel acetate, nickel sulfate, ammonium nickel sulfate, nickel chloride, nickel nitrate, nickel oxalate and nickel bromide.
Wherein the transitional die cavity filler is one or more of calcium hydroxide, calcium oxide and calcium carbonate; the transitional die cavity filler can also be mixed into the product obtained in the step (a) in a grinding or ball milling mode, and then the mixed product is added into a pore-expanding agent solution and is dried after being stirred; the mass ratio of the transitional cavity filler to the resin is 0.1-10 kg/kg.
Wherein the pore-expanding agent is one or more of potassium hydroxide, sodium hydroxide or calcium hydroxide; the pore-expanding agent can be mixed into a transitional die cavity filler solution added with resin for adsorbing metal ions in a form of ethanol saturated solution or suspension stirring and mixing; the mass ratio of the pore-expanding agent to the resin is 0.1-5 kg/kg.
Wherein the transitional mold cavity filler: the pore-expanding agent: the mass ratio of the resin is 0.1-10: 0.1-5: 1.
wherein the technological parameters of the heat treatment are as follows: heating to 500-1100 deg.C at a heating rate of 1-10 deg.C/min, maintaining at the temperature for 0.1-6h, and cooling to room temperature at a cooling rate of 1-10 deg.C/min.
In the step (d), the acid adopted in the acid washing is hydrochloric acid or nitric acid, and the soaking time is 24-72 hours; the drying temperature is 60-250 ℃, and the drying time is 24-72 h.
The preparation method takes porous large-mesh resin with wide sources and low cost as a carbon source and a self-template, takes transition metal as a low-temperature graphitization catalyst, adds a certain amount of filler and pore-creating/pore-expanding agent which play a role in pore space transitional filling and activating, carries out pyrolysis through heat treatment, realizes in-situ carbonization, graphitization, pore-enlarging and pore-expanding of the carbon source and the self-template, and then cleans off non-carbon residues to prepare the porous graphitization carbon material with the three-dimensional structure. The graphitized carbon material with the three-dimensional structure is a multi-level open pore self-supporting structure with micropores (the pore diameter is less than 2nm), mesopores (2-50 nm), macropores (larger than 50nm) and micron-sized macroscopic pores, has the characteristics of adjustable and controllable pore structures and distribution, large specific surface area, high porosity, high conductivity, low density, difficulty in re-stacking and the like, and has a wide application prospect. The preparation process is simple and easy to implement, later template etching is not needed, non-carbon residues are easy to remove, the cost is low, part of raw materials can be recycled, and large-scale production is easy to realize.
The method for coating the negative electrode material including the negative electrode active material, the conductive agent and the binder on the current collector is not particularly limited, and may be performed by a method generally used in the art, such as preparing the negative electrode active material, the conductive agent and the binder into a negative electrode slurry, and then coating the negative electrode slurry on the current collector.
As one embodiment of the present invention, there is provided a secondary battery including a positive electrode, a negative electrode, and an electrolytic solution, wherein the negative electrode includes at least one of the above-described negative electrode active materials.
The positive electrode and the electrolyte are not particularly limited, and a conventional positive electrode and electrolyte in the field of nonaqueous secondary batteries may be selected, for example, a positive electrode sheet coated with a positive electrode active material may be selected as the positive electrode, and the positive electrode active material may be one or more selected from a lithium composite oxide of nickel cobalt manganese, a lithium composite oxide of nickel cobalt manganese, a lithium composite oxide of nickel manganese, and lithium iron phosphate. In addition, the positive electrode can also adopt a lithium sheet, a potassium sheet or a sodium sheet to be respectively applied to a lithium ion battery, a potassium ion battery or a sodium ion battery. The electrolyte of the lithium battery can be LiPF6, the electrolyte of potassium electricity can be KPF6, the electrolyte of sodium electricity can be NaPF6, and the solvent can be a solvent with the volume ratio of 1: 1 (EC) and Ethyl Methyl Carbonate (EMC).
The present invention will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Firstly, preparing an open pore three-dimensional structure graphitized carbon material (HPGC) with multi-level pore diameter distribution, and the steps are as follows:
1. adding 50g of the pretreated macroporous acrylic ion exchange resin into 200ml of 0.2mol/L cobalt chloride aqueous solution, stirring for 2 hours, putting into 80 ℃ water bath, stirring, evaporating to dryness, drying by blowing at 80 ℃ for 12 hours, and crushing to obtain a resin for adsorbing cobalt ions;
2. dissolving 100g of potassium hydroxide in 400ml of absolute ethanol to form a potassium hydroxide/ethanol solution, dissolving 100g of calcium hydroxide in 400ml of water to form a calcium hydroxide/water solution, adding the products obtained in the step 1 into the potassium hydroxide/ethanol solution and the calcium hydroxide/water solution respectively, mixing the solutions, putting the mixed solution into an oil bath at 80 ℃, stirring and evaporating the mixed solution until the mixed solution is pasty, drying the mixed solution at 80 ℃, and then crushing the mixed solution again;
3. heating the product obtained in the step 2 to 800 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the heat for 2 hours, and naturally cooling to room temperature;
4. and (3) soaking the product obtained in the step (3) in 1mol/L hydrochloric acid solution for 36 hours, filtering, drying at 60 ℃ for 36 hours, and continuously drying at 150 ℃ for 8 hours to obtain the porous graphitized carbon material.
As shown in fig. 10-12, SEM (fig. 10), 200nm size TEM (fig. 11) and BET pore size distribution diagram (fig. 12) analysis results and BET pore size distribution diagram (fig. 12) test results of the graphitized carbon material (HPGC) show that a porous three-dimensional structure exists in a graphitized carbon material (HPGC) sample, and the porous three-dimensional structure includes a plurality of interconnected micropores (≦ 2nm), mesopores (2-50 nm), macropores (50-100 nm) and micron-sized macroscopic pores.
Example 1:
dispersing porous graphitized carbon in a 2mol/L sodium hydroxide aqueous solution by ultrasonic waves, then putting the porous graphitized carbon into a high-pressure hydrothermal kettle, carrying out hydrothermal reaction for 2 hours at 180 ℃, carrying out suction filtration and cleaning on the obtained substance by using deionized water until the pH value is 7, and putting the substance into an oven for drying.
Taking out 100mg of the functionalized porous carbon material, dispersing the functionalized porous carbon material in ethylene glycol solution, ultrasonically stirring for half an hour, sequentially adding stannous chloride and thiourea, and sequentially adding water at 100 ℃ and 200 ℃ respectivelyPerforming thermal reaction, respectively keeping the temperature for 10h, performing suction filtration and cleaning on the obtained substances for four times by using deionized water and ethanol, and drying. The obtained material is a composite material (HPGC-SnS) of porous graphitized carbon surface loaded with tin disulfide nano particles2) Wherein the ratio of tin disulfide is about 60 wt%.
Fig. 1 shows the XRD pattern of tin disulfide. FIG. 2 FIG. 3 is a HPGC/SnS2TEM pictures of (a). It can be seen that the tin disulfide small particles of 2-3nm are uniformly loaded on the surface of the graphitized carbon.
Example 2
Dispersing porous graphitized carbon in 2mol/L sodium hydroxide by ultrasonic waves, then putting the porous graphitized carbon into a high-pressure hydrothermal kettle, carrying out hydrothermal reaction for 2 hours at 180 ℃, carrying out suction filtration and cleaning on the obtained substance by using deionized water until the pH value is 7, and putting the substance into an oven for drying.
Taking out 100mg of the functionalized porous carbon material, dispersing the functionalized porous carbon material in an ethylene glycol solution, ultrasonically stirring for half an hour, sequentially adding stannous chloride and thiourea, performing hydrothermal reaction at 100 ℃ and 200 ℃ respectively, keeping the temperature for 10 hours respectively, performing suction filtration and cleaning on the obtained substance for four times by using deionized water and ethanol, and drying. The obtained material is a negative active substance (HPGC-SnS) of porous graphitized carbon surface loaded with tin disulfide nano particles2)。
Introducing HPGC-SnS2Heating to 500 ℃ in nitrogen atmosphere, keeping the temperature for 1 hour, carrying out heat treatment reaction on the tin disulfide to generate a tin sulfide nanorod, and showing an XRD (X-ray diffraction) diagram of the tin sulfide in figure 4 and a TEM (transverse electric field) picture of HPGC/SnS in figure 5, wherein the length of the tin sulfide nanorod is about 100-200nm and the diameter of the tin sulfide nanorod is about 20-40nm, and the tin sulfide nanorod is partially embedded into the hole of the porous graphitized carbon material.
Coating the negative electrode active material obtained in the above example 1-2, a conductive agent (carbon nanotube) and a binder (CMC) at a certain ratio (7:2:1), controlling the coating thickness at 100um, drying in a vacuum oven at 60 ℃, cutting the obtained diaphragm into pieces, weighing, and obtaining the coating layer with the mass of about 0.8mg/cm on each diaphragm2。
Meanwhile, in order to illustrate the advantages of the anode of the present invention, the inventors also performed the following comparative tests:
comparative example 1:
example 1 No functionalized HPGC was added during the synthesis, and the other processes were all the same, to obtain SnS2Substance, denoted SnS2. FIG. 6 shows SnS2SEM of (5) is micron-sized particles, shows no addition of HPGC, SnS in the synthesis process2Easy to agglomerate.
Comparative example 2:
and (3) heating the material in the comparative example 1 to 500 ℃, carrying out heat treatment, and keeping the temperature for 1h to obtain SnS, which is recorded as SnS, wherein an SEM of the SnS is shown in figure 7. The particles are larger.
Comparative example 3:
the negative electrode test was performed directly by HPGC without addition of tin sulfide.
FIG. 8 shows the cycling performance of examples 1, 2 and comparative examples 1, 2, 3 at 0.5A/g in a lithium battery system, from which HPGC-SnS can be seen2And the cycle capacity of HPGC/SnS is superior to that of the negative electrodes of the other three comparative examples; among them, the circulating capacity of HPGC/SnS is most prominent. FIG. 9 shows the rate charge and discharge performance, also HPGC-SnS2And HPGC/SnS is superior to other three types of negative electrode materials of comparative examples, wherein the rate performance of the HPGC/SnS is most outstanding.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (14)

1. The negative electrode of the secondary battery comprises a current collector and a negative electrode material coated on the current collector, and is characterized in that the negative electrode material comprises a negative electrode active substance, a conductive agent and a binder, wherein the negative electrode active substance comprises a graphitized carbon material with an open pore three-dimensional structure and multi-level pore size distribution, and tin-based materials of nano-scale particles are loaded on the surface of the graphitized carbon material.
2. The secondary battery anode of claim 1, wherein the tin-based material comprises tin disulfide nanoparticles having an average particle size of 2-5 nm.
3. The negative electrode for a secondary battery according to claim 1, wherein the tin-based material comprises tin sulfide nanorods, and the tin sulfide nanorods have an average length of 50 to 200nm and an average diameter of 10 to 50 nm.
4. The negative electrode for a secondary battery according to claim 1, wherein the graphitized carbon material comprises a multi-layered open pore self-supporting three-dimensional structure of micropores with a pore diameter of less than 2nm, mesopores with a pore diameter of 2-50nm, macropores in nanometer order with a pore diameter of more than 50nm, and macroscopic pores in micrometer order.
5. The negative electrode for a secondary battery according to claim 1, wherein the weight ratio of the negative electrode active material is 55 to 95%, the weight ratio of the conductive agent is 2 to 15%, and the weight ratio of the binder is 3 to 30%.
6. The negative electrode for a secondary battery according to claim 5, wherein the weight ratio of the negative electrode active material is 60 to 80%, and the total weight ratio of the conductive agent and the binder is 20 to 40%.
7. A preparation method of a secondary battery cathode is characterized by comprising the following steps:
coating a negative electrode material including a negative electrode active material, a conductive agent and a binder on a current collector, wherein the negative electrode active material is prepared by the steps of:
(1) dispersing the graphitized carbon material with an open pore three-dimensional structure with multi-level pore size distribution in a strong acid or strong alkali solution, carrying out hydrothermal reaction, filtering a reaction product, washing the reaction product to be neutral by using deionized water, and drying the reaction product to obtain a functionalized graphitized carbon material;
(2) dispersing the functional graphitized carbon material in a solvent, stirring, adding a tin source and a sulfur source, carrying out hydrothermal reaction, filtering and cleaning a reaction product, and drying to obtain the negative active material.
8. The method for preparing a secondary battery anode according to claim 7, wherein the graphitized carbon material having an open pore three-dimensional structure with a plurality of layers of pore size distribution is prepared by:
(a) mixing the large-mesh resin with a metal ion salt solution, stirring, drying, and crushing to obtain a resin capable of adsorbing metal ions; (b) respectively preparing a transitional die cavity filler aqueous solution and a pore-expanding agent solution, respectively adding the resin for adsorbing the metal ions into the transitional die cavity filler solution and the pore-expanding agent solution, mixing the solutions, stirring, drying, and crushing again; (c) carrying out heat treatment on the product obtained in the step (b) in an inert gas atmosphere; (d) and (c) carrying out acid washing, filtering and drying on the product obtained in the step (c) to obtain the three-dimensional structure graphitized carbon material with multi-level open pores with pore diameter distribution.
9. The method for producing a secondary-battery anode according to claim 7, characterized in that the production of the anode active material further comprises step (3): and (3) carrying out heat treatment on the negative electrode active material obtained in the step (2) in an inert atmosphere, wherein the heat treatment temperature is 400-500 ℃, and the time is 1-3 h.
10. The method for preparing the negative electrode of the secondary battery as claimed in claim 7, wherein the strong base in the step (1) is sodium hydroxide or potassium hydroxide, the strong acid is sulfuric acid or nitric acid, the concentration is 2-6mol/L, the hydrothermal reaction temperature is 100-200 ℃, and the time is 2-6 h.
11. The method for preparing the negative electrode of the secondary battery as claimed in claim 7, wherein the solvent in the step (2) is selected from ethylene glycol, ethanol, polyethylene glycol or water, the stirring is ultrasonic stirring, the stirring time is 0.5-2h, the tin source is at least one of tin chloride and stannous chloride, the sulfur source is at least one of thiourea, sodium sulfide and sodium thiosulfate, and the hydrothermal reaction temperature is 100-220 ℃ and the hydrothermal reaction time is 10-24 h.
12. The method for preparing the negative electrode of the secondary battery as claimed in claim 11, wherein the solvent is selected from ethylene glycol, ethanol or polyethylene glycol, and the hydrothermal reaction temperature is 160-220 ℃ and the time is 20-24 h.
13. A secondary battery comprising a positive electrode, a negative electrode and an electrolytic solution, characterized in that the negative electrode comprises the negative electrode according to any one of claims 1 to 6.
14. Use of the secondary battery anode according to any one of claims 1 to 6 in a lithium ion secondary battery, a potassium ion secondary battery, or a sodium ion secondary battery.
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