CN111777414B - Carbon negative electrode material precursor, preparation method and application thereof, carbon negative electrode material, preparation method and application thereof - Google Patents

Carbon negative electrode material precursor, preparation method and application thereof, carbon negative electrode material, preparation method and application thereof Download PDF

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CN111777414B
CN111777414B CN202010587696.8A CN202010587696A CN111777414B CN 111777414 B CN111777414 B CN 111777414B CN 202010587696 A CN202010587696 A CN 202010587696A CN 111777414 B CN111777414 B CN 111777414B
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coal
negative electrode
precursor
carbon
electrode material
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CN111777414A (en
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张留峰
郭培瑞
唐杰
孙占龙
杨生斌
徐秀丽
唐帅
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Shanxi Qinxin Energy Group Co Ltd
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/063—Preparing or treating the raw materials individually or as batches
    • C04B38/0635—Compounding ingredients
    • C04B38/0645—Burnable, meltable, sublimable materials
    • C04B38/068—Carbonaceous materials, e.g. coal, carbon, graphite, hydrocarbons
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522—Graphite
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the technical field of lithium ion batteries, in particular to a carbon negative electrode material precursor, a preparation method and application thereof, and a carbon negative electrode material, a preparation method and application thereof. The carbon negative electrode material precursor is obtained by performing heat treatment on a mixture of high-order bituminous coal, a coal-based binder, a coal-based inert agent and an additive; wherein the high-order bituminous coal is bituminous coal with vitrinite average reflectivity of more than 1.3 percent and is selected from high-order coking coal and/or lean coal. The invention adopts high-order bituminous coal, coal-based binder and coal-based inert agent which have wide sources and low price, on one hand, the carbon source of the precursor is enlarged, and the production cost is reduced; meanwhile, the addition of the additive effectively improves the pore structure of the precursor, and further improves the electrochemical performance of the carbon cathode material prepared from the precursor.

Description

Carbon negative electrode material precursor, preparation method and application thereof, carbon negative electrode material, preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a carbon negative electrode material precursor, a preparation method and application thereof, and a carbon negative electrode material, a preparation method and application thereof.
Background
The most widely used battery negative electrode material is graphitized carbon material, and among graphitized carbon negative electrode materials, the artificial graphite has long cycle life and good rate capability and is mostly used for power lithium batteries. The raw materials for producing the carbon cathode material by using the artificial graphite mainly comprise high-end carbon materials such as needle coke, mesocarbon microbeads and the like, the raw materials belong to products which are in short supply at home and abroad, the market shows a situation of short supply, the cost is high, and the quality is also different. The cathode material is produced by depending on outsourcing raw materials, so that the production cost of enterprises is overhigh and the production is unstable. However, the carbon cathode material precursor produced by the existing carbon cathode precursor production technology is difficult to graphitize, has high thermal expansion coefficient and low porosity, and the cathode material obtained by the graphitization has poor electrochemical performance, so that the development of the carbon cathode material precursor which can stably control the quality and has higher cost performance and the preparation technology thereof is great.
Disclosure of Invention
The invention aims to solve the problems of difficult graphitization, high thermal expansion coefficient, low porosity and the like of a carbon negative electrode material precursor, the problems of shortage of raw materials, high cost and the like in the prior art, and provides a carbon negative electrode material precursor, a preparation method and application thereof, a carbon negative electrode material, a preparation method and application thereof. The precursor has the characteristics of low ash content, low sulfur content, high fixed carbon content and the like, improves the graphitization degree and the porosity of the precursor, thereby improving the electrochemical performance of the carbon cathode material, has wide carbon source and low price, and is simple to prepare and convenient for industrial production.
In order to achieve the above object, a first aspect of the present invention provides a precursor of a carbon negative electrode material, wherein the precursor is obtained by heat-treating a mixture of high-order bituminous coal, a coal-based binder, a coal-based inert agent and an additive; wherein the high-order bituminous coal is bituminous coal with vitrinite average reflectivity of more than 1.3 percent and is selected from high-order coking coal and/or lean coal.
Preferably, the weight ratio of the high-order bituminous coal, the coal-based binder, the coal-based inert agent and the additive is 25-45: 15-35: 25-45: 0.2 to 3, preferably 30 to 45: 20-35: 30-45: 0.5 to 3, more preferably 35 to 40: 20-30: 35-40: 0.5-2.
Preferably, the parameters of the carbon anode material precursor satisfy: ash content is less than 3 wt%, sulfur content is less than 0.5 wt%, and fixed carbon content is more than 96 wt%.
The second aspect of the present invention provides a method for preparing a precursor of a carbon negative electrode material, including the steps of:
(1) mixing and molding high-order bituminous coal, a coal-based binder, a coal-based inert agent and an additive to obtain a material cake;
(2) sequentially carrying out heat treatment, cooling and granule finishing on the material cake to obtain a carbon negative electrode material precursor;
wherein the high-order bituminous coal is bituminous coal with vitrinite average reflectivity of more than 1.3 percent and is selected from high-order coking coal and/or lean coal.
Preferably, in step (1), the mixing comprises: and respectively crushing the high-order bituminous coal, the coal-based binder and the coal-based inert agent, and then mixing the crushed high-order bituminous coal, the coal-based binder and the coal-based inert agent with the additive.
Preferably, in the step (2), the heat treatment includes: a first stage, a second stage, a third stage, and a fourth stage.
The third aspect of the invention provides an application of the carbon negative electrode material precursor provided by the first aspect and/or the carbon negative electrode material precursor prepared by the method provided by the second aspect in a carbon negative electrode material.
The fourth aspect of the present invention provides a method for producing a carbon anode material, the method comprising: and carrying out graphitization treatment on the provided carbon negative electrode material precursor and/or the carbon negative electrode material precursor prepared by the method provided by the second aspect to obtain the carbon negative electrode material.
The fifth aspect of the invention provides a carbon negative electrode material prepared by the method provided by the fourth aspect.
The invention in a sixth aspect provides a carbon negative electrode material prepared by the method in the fourth aspect and/or an application of the carbon negative electrode material in a lithium ion battery.
Compared with the method that refined asphalt is adopted as the carbon source of the carbon cathode material precursor, the method adopts high-order bituminous coal, coal-based binder and coal-based inert agent which are wide in source and low in price, so that the carbon source of the precursor is expanded, and the production cost is reduced; meanwhile, due to the addition of the additive, the prepared precursor is easier to graphitize, and the pore structure of the precursor is effectively improved, so that the electrochemical performance of the carbon cathode material is improved. In addition, the preparation process of the carbon cathode material precursor provided by the invention is simple, short in flow, safe and reliable, and convenient for industrial production, and the process is free of variable-pressure treatment.
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.
The invention provides a carbon negative electrode material precursor, which is obtained by carrying out heat treatment on a mixture of high-order bituminous coal, a coal-based binder, a coal-based inert agent and an additive; wherein the high-order bituminous coal is bituminous coal with vitrinite average reflectivity of more than 1.3 percent and is selected from high-order coking coal and/or lean coal.
The inventor of the invention finds in research that: the method comprises the following steps of taking a mixture of high-order bituminous coal, a coal-based binder and a coal-based inert agent as a carbon source of a precursor of a carbon negative electrode material, wherein the coal-based inert agent has ultralow ash content, ultralow sulfur content, compact structure, good carbon layer orientation and balanced caking property of a material cake, and is softened and melted in the preparation process of the precursor to promote the conversion and ordered rearrangement of the high-order bituminous coal and the coal-based binder; the high-order bituminous coal has high deterioration degree, the aromaticity and the condensation degree of a coal macromolecular structure are high, a carbon atom layer has good preferred orientation, the structure is compact, and the high-order bituminous coal is easy to graphitize at high temperature; the high-order bituminous coal has certain caking property, the coking process can be gradually coked, and the pore structure of the high-order bituminous coal can be adjusted through the slow coking process. Therefore, by reasonably regulating and controlling the weight ratio of the high-order bituminous coal, the coal-based binder, the coal-based inert agent and the additive, the precursor of the carbon negative electrode material which is easier to graphitize can be obtained through heat treatment, the pore structure of the precursor is effectively improved, and the electrochemical performance of the carbon negative electrode material prepared from the precursor is further improved.
According to the present invention, preferably, the weight ratio of the high-rank bituminous coal, the coal-based binder, the coal-based inert agent and the additive is 25-45: 15-35: 25-45: 0.2 to 3, preferably 30 to 45: 20-35: 30-45: 0.5 to 3, more preferably 35 to 40: 20-30: 35-40: 0.5-2. The preferable weight ratio is adopted, so that the performance of the precursor is improved.
Preferably, the parameters of the carbon anode material precursor satisfy: ash content is less than 3 wt%, sulfur content is less than 0.5 wt%, and fixed carbon content is more than 96 wt%. The invention adopts high-order bituminous coal, coal-based binder, coal-based inert agent and additive as the source of the precursor, and expands the source of the precursor while ensuring the parameters of the precursor.
Preferably, the parameters of the high-rank bituminous coal satisfy: the coal-rock composite material comprises, by weight, not more than 8% of ash, not more than 0.6% of sulfur, not more than 20% of volatile matter, not less than 55% of bonding index, not less than 25mm of colloidal layer index, not less than 1.2 of coal-rock activity-inertia ratio, not less than 3% of catalytic index and 8-15% of water, wherein the colloidal layer index of less than 25mm means that the colloidal layer index X and the colloidal layer index Y are independently less than 25 mm.
In a preferred embodiment, the high-order bituminous coal is high-order coking coal and lean coal, wherein the weight ratio of the high-order coking coal to the lean coal is 20-50: 5-15.
In the invention, the high-order bituminous coal has higher metamorphic grade, aromaticity and condensation grade, the carbon atom layer has certain cohesive property, the carbonization process can be gradually coked, and the pore structure of the precursor can be improved through the slow carbonization process.
In the present invention, the TI is a toluene-insoluble component in coal tar pitch and/or the like, and QI is quinoline insoluble matter, unless otherwise specified.
Preferably, the parameters of the coal-based binder satisfy: ash content is less than 0.5 wt%, sulfur content is less than 0.2 wt%, volatile content is less than 60 wt%, coking value is more than 40%, TI content is more than 25 wt%, QI content is less than 20 wt%, softening point content is more than 100 deg.C, and water content is 5-10 wt%; further preferably, the base binder is pitch, preferably at least one selected from coal tar high temperature pitch, coal tar medium temperature pitch, coal base mesophase pitch, coal tar refined pitch and coal liquefaction residual pitch.
Preferably, the parameters of the coal-based inert agent satisfy: ash content is less than 0.5 wt%, sulfur content is less than 0.5 wt%, volatile content is less than 15 wt%, and water content is 5-15 wt%; further preferably, the coal-based inert agent is selected from at least one of anthracite, pitch coke, and petroleum coke.
In the present invention, in order to further improve the pore structure of the precursor, preferably, the additive is selected from a graphitization catalyst and a carbon pore modifier; further preferably, the additive comprises 20-50 wt% of graphitization catalyst and 50-80 wt% of carbon pore modifier.
Preferably, the graphitization catalyst comprises optional aluminosilicic acid, optional iron powder and silicon carbide, wherein the molecular formula of the aluminosilicic acid is Na2Al2O3·2SiO2·nH2O, wherein n is selected from any number from 1 to 5; further preferably, the weight ratio of the aluminum substituted silicic acid to the iron powder to the silicon carbide is 0-15: 0-5: 80-100, preferably 5-15: 3-5: 80-92.
In a preferred embodiment of the present invention, the graphitization catalyst comprises aluminosilicic acid, iron powder, and silicon carbide, wherein the weight ratio of the aluminosilicic acid to the iron powder to the silicon carbide is 5-15: 3-5: 80-92.
Preferably, the char pore modifier comprises potassium nitrate and optionally calcium nitrate; further preferably, the weight ratio of potassium nitrate to calcium nitrate is 60-100: 0 to 40; preferably 75 to 90: 10-25.
In a preferred embodiment of the present invention, the carbon pore modifier comprises potassium nitrate and calcium nitrate, wherein the weight ratio of potassium nitrate to calcium nitrate is 75-90: 10-25.
In the invention, the additive can catalyze the conversion of the carbon source to the ordered crystal form at a higher heat treatment temperature (more than 1200 ℃), namely, the graphitization degree of the product is effectively improved; meanwhile, the additive can activate a carbon source (namely, a mixture of high-order bituminous coal, a coal-based binder and a coal-based inert agent) at room temperature to 900 ℃, so that the porosity of the carbon surface is directionally increased, namely, the proportion of micropores and mesopores is increased, and the lithium storage capacity of the precursor is improved.
The second aspect of the present invention provides a method for preparing a precursor of a carbon negative electrode material, the method comprising the steps of:
(1) mixing and molding high-order bituminous coal, a coal-based binder, a coal-based inert agent and an additive to obtain a material cake;
(2) sequentially carrying out heat treatment, cooling and granule finishing on the material cake to obtain a carbon negative electrode material precursor;
wherein the high-order bituminous coal is bituminous coal with vitrinite average reflectivity of more than 1.3 percent and is selected from high-order coking coal and/or lean coal.
In the invention, the mixing in the step (1) has a wide selection range, and the high-order bituminous coal, the coal-based binder, the coal-based inert agent and the additive are uniformly mixed. Preferably, in step (1), the mixing comprises: and respectively crushing the high-order bituminous coal, the coal-based binder and the coal-based inert agent, and then mixing the crushed high-order bituminous coal, the coal-based binder and the coal-based inert agent with the additive. And the preferable conditions are adopted to prevent the coal-based binder from being excessively crushed, causing the coal-based binder to be thermally bonded and blocking crushing equipment.
In the present invention, the step of separately pulverizing the high-rank bituminous coal, the coal-based binder and the coal-based inert agent means that the high-rank bituminous coal, the coal-based binder and the coal-based inert agent are independently pulverized.
In a preferred embodiment of the present invention, after pulverization, the high rank bituminous coal has more than 90% of particles with a particle size of less than 1.5 mm; after being crushed, the coal-based binder accounts for more than 90 percent of particles with the granularity less than 3 mm; after being crushed, the coal-based inert agent has more than 90 percent of particles with the particle size less than 1 mm.
Preferably, the comminution is carried out in a mill.
In the invention, the forming mode has a wide selection range, and only high-order bituminous coal, coal-based binder and coal-based inert agent which are uniformly mixed are formed. Preferably, the forming is performed in a forming machine. The forming conditions have a wide range of options as long as the density and moisture of the formed cake meet the requirements.
According to the invention, preferably, the cake has a density of 1-2t/m3Preferably 1.1 to 1.5t/m3The moisture content of the material cake is 5-15 wt%, preferably 7-12 wt%. And the preferable conditions are adopted, so that the pore structure of the precursor is improved.
Preferably, in the step (2), the heat treatment includes: a first stage, a second stage, a third stage, and a fourth stage. The material cake is subjected to four-stage heat treatment, so that the parameters of the precursor can be improved, and the electrochemical performance of the precursor can be improved.
Further preferably, the conditions of the first stage include: the temperature is more than 100 ℃ and not more than 300 ℃, preferably more than 150 ℃ and not more than 250 ℃; the time is 40-60h, preferably 45-55 h. The purpose of the first stage is to dry the moisture in the cake and increase the thermal conductivity of the cake.
Further preferably, the conditions of the second stage include: the temperature is more than 300 ℃ and not more than 700 ℃, preferably more than 400 ℃ and not more than 600 ℃; the time is 70-90h, preferably 75-85 h. The second stage aims at reducing shrinkage stress in the material cake carbonization process and improving the fusion degree of materials in the material cake.
Further preferably, the conditions of the third stage include: the temperature is greater than 700 ℃ and not greater than 950 ℃, preferably greater than 800 ℃ and not greater than 950 ℃. The third stage aims to activate the mixed carbon source, increase the porosity of the precursor directionally and improve the lithium storage capacity of the precursor.
Further preferably, the conditions of the fourth stage include: the temperature is greater than 950 ℃ and not greater than 1500 ℃, preferably greater than 950 ℃ and not greater than 1350 ℃. The fourth stage aims at catalyzing a mixed carbon source (namely, a mixture of high-order bituminous coal, a coal-based binder and a coal-based inert agent) to perform ordered crystal form conversion and improving the graphitization degree of the precursor.
According to the present invention, preferably, the weight ratio of the high-rank bituminous coal, the coal-based binder, the coal-based inert agent and the additive is 25-45: 15-35: 25-45: 0.2 to 3, preferably 30 to 45: 20-35: 30-45: 0.5 to 3, more preferably 35 to 40: 20-30: 35-40: 0.5-2.
In the present invention, the parameter properties and specific types of the high-rank bituminous coal, the coal-based binder, the coal-based inert agent and the additive are defined as above, and the detailed description thereof is omitted.
In the present invention, the cooling method and conditions are not limited as long as the heat-treated product is cooled to room temperature.
In the present invention, the size control is performed in a size controller for classifying and adjusting the precursor.
The third aspect of the invention provides an application of the carbon negative electrode material precursor provided by the first aspect and/or the carbon negative electrode material precursor prepared by the method provided by the second aspect in a carbon negative electrode material.
The carbon negative electrode material precursor provided by the invention has the characteristics of low ash content, low sulfur content, high fixed carbon content and easy graphitization, effectively improves the pore structure of the precursor, and further improves the electrochemical performance of the carbon negative electrode material prepared from the precursor.
A fourth aspect of the present invention provides a method for producing a carbon negative electrode material, the method including: and carrying out graphitization treatment on the provided carbon negative electrode material precursor and/or the carbon negative electrode material precursor prepared by the method provided by the second aspect to obtain the carbon negative electrode material.
According to the present invention, preferably, the graphitization treatment conditions include: the temperature is more than or equal to 2500 ℃, preferably 2500-3200 ℃, and the time is 10-60h, preferably 30-55 h. And the preferable conditions are adopted, so that the electrochemical performance of the carbon negative electrode material is improved.
The fifth aspect of the invention provides a carbon negative electrode material prepared by the method provided by the fourth aspect.
According to the present invention, preferably, the carbon anode material has parameters satisfying: the degree of graphitization is more than 90%, and the coefficient of thermal expansion is less than 1.7 multiplied by 105The porosity is more than 10% and the pore diameter less than 50nm accounts for more than 40%. Namely, the carbon negative electrode material provided by the invention has the characteristics of high graphitization degree, low thermal expansion coefficient, high porosity and easiness in lithium storage, and the electrochemical performance of the carbon negative electrode material is effectively improved.
The invention in a sixth aspect provides a carbon negative electrode material prepared by the method in the fourth aspect and/or an application of the carbon negative electrode material in a lithium ion battery.
The present invention will be described in detail below by way of examples.
The parameters of the A coal (high-rank coking coal) meet the following conditions: the average reflectivity of vitrinite is more than 1.5 percent, the ash content is 6.02 percent by weight, the sulfur content is 0.52 percent by weight, the volatile content is 17.45 percent by weight, the bonding index is 84, the colloidal layer index X is 17mm, the colloidal layer index Y is 10mm, the coal-rock activity-inertia ratio is 0.98, the catalytic index is 1.95 percent, and the water content is 12 percent by weight;
the parameters of the coal B (lean coal) meet the following conditions: the average reflectivity of vitrinite is more than 1.5 percent, the ash content is 7.41 percent by weight, the sulfur content is 0.41 percent by weight, the volatile content is 16.49 percent by weight, the bonding index is 70, the colloidal layer index X is 18mm, the colloidal layer index Y is 6.5mm, the coal-rock activity-inertia ratio is 0.46, the catalytic index is 1.88 percent, and the water content is 10 percent by weight;
the parameters of the high-temperature asphalt meet the following requirements: ash content 0.15 wt%, sulfur content 0.06 wt%, volatile content 11.13 wt%, coking value 45.36%, TI content 29.5 wt%, QI content 12.27 wt%, softening point content 117 deg.C, moisture content 6 wt%;
The parameters of the pitch coke meet the following conditions: the ash content was 0.15 wt%, the sulfur content was 0.15 wt%, the volatile content was 10.26 wt%, and the moisture content was 10 wt%.
The conditions for preparing the carbon anode material precursors in examples 1 to 9 and comparative examples 1 to 4 are shown in table 1; the parameters of the carbon anode material precursors obtained in examples 1 to 9 and comparative examples 1 to 4 are shown in table 2.
Example 1
(1) The additive H-1 comprises 30 wt% of graphitization catalyst and 70 wt% of carbon pore modifier, wherein the weight ratio of aluminosilicate, iron powder and silicon carbide in the graphitization catalyst is 10:5:85, and the weight ratio of potassium nitrate to calcium nitrate in the carbon pore modifier is 80: 20;
(2) mixing and molding the crushed coal A, the crushed coal B, the crushed bituminous coke and the crushed high-temperature asphalt with an additive H-1 to obtain a material cake, wherein the weight ratio of the coal A to the coal B is 25: 14.5;
(3) and performing heat treatment, cooling and size stabilization on the material cake to obtain the carbon negative electrode material precursor S1, wherein the heat treatment comprises a first stage, a second stage, a third stage and a fourth stage.
Example 2
(1) 92% of crushed coal A and crushed coal B, 95% of crushed asphalt coke, 90% of crushed high-temperature asphalt, 50% of graphitized catalyst and 50% of carbon pore modifier, wherein the weight ratio of aluminosilicate, iron powder and silicon carbide in the graphitized catalyst is 15:5:80, and the weight ratio of potassium nitrate to calcium nitrate in the carbon pore modifier is 90: 10;
(2) mixing and molding the crushed coal A, coal B, pitch coke and high-temperature asphalt with an additive H-2 to obtain a material cake, wherein the weight ratio of the coal A to the coal B is 30: 10;
(3) and performing heat treatment, cooling and size stabilization on the cake to obtain the carbon negative electrode material precursor S2, wherein the heat treatment comprises a first stage, a second stage, a third stage and a fourth stage.
Example 3
(1) 98 percent of particles with the particle size of the crushed coal A being less than 1.5mm, 97 percent of particles with the particle size of the crushed asphalt coke being less than 1mm, 95 percent of particles with the particle size of the crushed high-temperature asphalt being less than 3mm, and the additive H-3 comprises 20 percent by weight of graphitization catalyst and 80 percent by weight of carbon pore modifier, wherein the weight ratio of aluminosilicate, iron powder and silicon carbide in the graphitization catalyst is 5:3:92, and the weight ratio of potassium nitrate and calcium nitrate in the carbon pore modifier is 75: 25;
(2) Mixing and molding the crushed coal A, the pitch coke and the high-temperature pitch with an additive H-3 to obtain a material cake;
(3) and performing heat treatment, cooling and size stabilization on the material cake to obtain the carbon negative electrode material precursor S3, wherein the heat treatment comprises a first stage, a second stage, a third stage and a fourth stage.
Example 4
The same procedure as in example 1 was repeated, except that the weight ratio of aluminosilicate, iron powder, and silicon carbide in the graphitization catalyst was changed to 0:0:100, and the weight ratio of potassium nitrate to calcium nitrate in the carbon pore modifier was changed to 100:0, to obtain a carbon negative electrode material precursor S4.
Example 5
The same procedure as in example 1 was repeated, except that the weight ratio of aluminosilicate, iron powder, and silicon carbide in the graphitization catalyst was changed to 20:15:65, and the weight ratio of potassium nitrate to calcium nitrate in the carbon pore modifier was changed to 50:50, to obtain a carbon negative electrode material precursor S5.
Example 6
The same procedure as in example 1 was repeated except that the coal a, the coal B, the high-temperature pitch, and the pitch coke were not pulverized, to obtain a carbon negative electrode material precursor S6.
Example 7
According to the method of example 1, except that the weight ratio of the high-order bituminous coal (coal a and coal B), the coal-based binder, the coal-based inert agent and the additive was changed to 45:15:39.8:0.2, the remaining steps were the same, and a carbon negative electrode material precursor S7 was obtained.
Example 8
According to the method of example 1, except that the weight ratio of the high-order bituminous coal (coal a and coal B), the coal-based binder, the coal-based inert agent and the additive was changed to 25:35:37:3, the remaining steps were the same, and the carbon negative electrode material precursor S8 was obtained.
Example 9
According to the method of example 1, except that the weight ratio of the high-order bituminous coal (coal a and coal B), the coal-based binder, the coal-based inert agent and the additive was changed to 50:20:25:5, the remaining steps were the same, and the carbon negative electrode material precursor S8 was obtained.
Comparative example 1
According to the method of example 1, except that the bituminous coal had a vitrinite average reflectance of 1.1%, the weight ratio of bituminous coal, coal-based binder, coal-based inert agent and additive was 39.5:20:40:0.5, the remaining steps were the same, and a carbon negative electrode material precursor D1 was obtained.
Comparative example 2
The same procedure as in example 1, except that pitch coke was not added, was repeated to obtain a carbon negative electrode material precursor D2.
Comparative example 3
The same procedure as in example 1, except that no high-temperature pitch was added, was repeated to obtain a carbon negative electrode material precursor D3.
Comparative example 4
High-quality coal-based needle coke D4 as a precursor of a carbon negative electrode material.
TABLE 1
Figure BDA0002554387560000141
Note: the weight ratio of the high-rank bituminous coal, the coal-based binder, the coal-based inert agent and the additive is defined; temperature/° c and time/h of the first, second, third and fourth stages.
TABLE 2
Precursor body Ash content, wt% Sulfur content, wt% Fixed carbon content, wt.%
Example 1 S1 2.11 0.32 98.24
Example 2 S2 2.22 0.38 96.33
Example 3 S3 2.13 0.36 98.17
Example 4 S4 2.14 0.33 98.27
Example 5 S5 2.12 0.35 98.38
Example 6 S6 2.25 0.37 98.24
Example 7 S7 2.54 0.49 98.41
Example 8 S8 2.97 0.46 98.20
Example 9 S9 2.14 0.35 98.18
Comparative example 1 D1 2.59 0.45 97.65
Comparative example 2 D2 9.53 0.58 96.48
Comparative example 3 D3 9.65 0.52 97.92
Comparative example 4 D4 0.07 0.03 97.66
The data in tables 1-2 show that the carbon negative electrode material precursor prepared by the method provided by the invention has the characteristics of low ash content, low sulfur content and high fixed carbon content, and the pore structure of the precursor is effectively improved.
Test example 1
The carbon negative electrode material precursors prepared in examples 1 to 9 and comparative examples 1 to 4 were subjected to electrochemical performance tests.
(1)Preparation of carbon negative electrode material: graphitizing the carbon negative electrode material precursors S1-9 and D1-4 to obtain carbon negative electrode materials PS1-9 and PD1-4, wherein the graphitizing treatment conditions comprise: the maximum temperature is 2800 ℃, the heat preservation time is 10h, wherein the parameters of the carbon negative electrode materials PS1-9 and PD1-4 are listed in Table 3;
(2)preparation of lithium ion Battery cathode: carbon negative electrode materials PS1-9 and PD1-4 are used as battery negative electrode materials, acetylene black is used as a conductive agent, polyvinylidene fluoride is used as a binder, wherein the weight ratio of the carbon negative electrode materials to the acetylene black to the polyvinylidene fluoride is 92:3:5, then 5 wt% of N-methyl-2-pyrrolidone solution is added, and the mixture is stirred for 30min at the speed of 1500r/min to form a paste. Uniformly coating the paste on a copper foil, baking for 8 hours in a vacuum oven at 100 ℃, and removing the solvent in the paste to obtain negative electrodes WS1-9 and WD1-4 of the battery;
(3)Assembled button cell: the negative pole WS1 of the battery-9 and WD1-4 as the negative electrode of the button cell, which was punched into a disc for use. And punching metal lithium into a round piece to be used as a positive electrode, separating the positive electrode and the negative electrode by adopting a polyethylene diaphragm, filling 1mol/L of ethylene carbonate/methyl ethyl carbonate (the volume ratio of the ethylene carbonate to the methyl ethyl carbonate is 1:1) solution of lithium hexafluorophosphate into the electrolyte, and assembling the battery in a glove box to operate to prepare the button cell.
The button cell is tested at 0.001-2V vs. Li/Li by adopting LAND CT2001+The first discharge specific capacity, the first coulombic efficiency and the cycle performance of the lithium secondary battery are tested in the voltage range of (1), and the test results are listed in table 4.
TABLE 3
Figure BDA0002554387560000171
Note: the number ratio of pores with pore diameter less than 50nm to all pores is percent.
The data in table 3 show that, compared with comparative examples 1 to 3, the carbon negative electrode material prepared from the precursor provided by the invention has a microporous structure which is low in thermal expansion coefficient, high in porosity and mostly uniform, is easy to store lithium, and effectively improves the electrochemical performance of the carbon negative electrode material. Compared with the comparative ratio 4, the parameters of the carbon negative electrode material provided by the invention are equivalent to those of the carbon negative electrode material obtained by graphitizing the existing high-quality coal-based needle coke.
TABLE 4
Figure BDA0002554387560000181
As can be seen from the data in table 4, when the carbon negative electrode material precursor provided by the present invention is applied to a lithium ion battery, the carbon negative electrode material precursor has excellent electrochemical properties, and particularly has high first lithium intercalation capacity, first lithium deintercalation capacity, 50-time post-cycle performance and coulombic efficiency, that is: the first lithium intercalation capacity reaches 380-400 mA.h/g, the first lithium deintercalation capacity is 345-360, the cycle performance after 50 times is 341-358 mA.h/g, and the coulomb efficiency is 90-92%. Compared with comparative examples 1-3, the carbon cathode material precursor provided by the invention has higher first lithium intercalation capacity and coulombic efficiency; compared with comparative example 4, the carbon cathode material precursor provided by the invention has the advantages of wide and cheap raw material source, equivalent electrical property and good product economy.
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 (29)

1. A carbon negative electrode material precursor is characterized in that the precursor is obtained by heat treatment of a mixture of high-order bituminous coal, a coal-based binder, a coal-based inert agent and an additive;
Wherein the high-order bituminous coal is bituminous coal with vitrinite average reflectivity of more than 1.3 percent, and is selected from high-order coking coal and/or lean coal;
wherein the additive comprises 20-50 wt% of graphitization catalyst and 50-80 wt% of carbon pore modifier;
wherein the weight ratio of the high-order bituminous coal, the coal-based binder, the coal-based inert agent and the additive is 25-45: 15-35: 25-45: 0.2-3;
wherein the parameters of the carbon negative electrode material precursor satisfy the following conditions: ash content is less than 3 wt%, sulfur content is less than 0.5 wt%, and fixed carbon content is more than 96 wt%.
2. The precursor of claim 1, wherein the weight ratio of the high-order bituminous coal, the coal-based binder, the coal-based inert agent, and the additive is 30-45: 20-35: 30-45: 0.5-3.
3. The precursor of claim 2, wherein the weight ratio of the high-order bituminous coal, the coal-based binder, the coal-based inert agent and the additive is 35-40: 20-30: 35-40: 0.5-2.
4. A precursor according to claim 2 wherein the parameters of the high-order bituminous coal satisfy: the ash content is less than or equal to 8 wt%, the sulfur content is less than 0.6 wt%, the volatile content is less than 20 wt%, the bonding index is greater than or equal to 55, the colloid layer index is less than 25mm, the coal-rock activity-inertness ratio is less than 1.2, the catalytic index is less than 3%, and the water content is 8-15 wt%; the parameters of the coal-based binder meet the following requirements: ash content is less than 0.5 wt%, sulfur content is less than 0.2 wt%, volatile content is less than 60 wt%, coking value is more than 40%, TI content is more than 25 wt%, QI content is less than 20 wt%, softening point content is more than 100 deg.C, and water content is 5-10 wt%;
The parameters of the coal-based inert agent meet the following requirements: ash content is less than 0.5 wt%, sulfur content is less than 0.5 wt%, volatile content is less than 15 wt%, and water content is 5-15 wt%.
5. A precursor according to any one of claims 1 to 4, wherein the coal-based binder is pitch.
6. The precursor according to claim 5, wherein the coal-based binder is selected from at least one of coal tar high temperature pitch, coal tar medium temperature pitch, coal-based mesophase pitch, coal tar refined pitch, and coal liquefaction residue pitch.
7. The precursor according to claim 5, wherein the coal-based inert agent is selected from at least one of anthracite, pitch coke, and petroleum coke.
8. A precursor according to claim 5 wherein the additive is selected from graphitization catalysts and carbon pore modifiers.
9. A method for preparing a precursor of a carbon negative electrode material, the method comprising the steps of:
(1) mixing and molding high-order bituminous coal, a coal-based binder, a coal-based inert agent and an additive to obtain a material cake;
(2) sequentially carrying out heat treatment, cooling and granule finishing on the material cake to obtain a carbon negative electrode material precursor;
wherein the high-order bituminous coal is a bituminous coal with vitrinite average reflectivity greater than 1.3%, and is selected from high-order coking coal and/or lean coal;
Wherein the additive comprises 20-50 wt% of graphitization catalyst and 50-80 wt% of carbon pore modifier;
wherein the weight ratio of the high-order bituminous coal, the coal-based binder, the coal-based inert agent and the additive is 25-45: 15-35: 25-45: 0.2-3;
wherein the parameters of the carbon negative electrode material precursor satisfy the following conditions: ash content is less than 3 wt%, sulfur content is less than 0.5 wt%, and fixed carbon content is more than 96 wt%.
10. The method of claim 9, wherein in step (1), the mixing comprises: and respectively crushing the high-order bituminous coal, the coal-based binder and the coal-based inert agent, and then mixing the crushed high-order bituminous coal, the coal-based binder and the coal-based inert agent with the additive.
11. The method of claim 10 wherein the high rank bituminous coal after pulverization has greater than 90% particles with a size < 1.5 mm; after being crushed, the coal-based binder accounts for more than 90 percent of particles with the granularity less than 3 mm; after being crushed, the coal-based inert agent has more than 90 percent of particles with the particle size less than 1 mm.
12. A method as claimed in claim 10, wherein the cake has a density of 1-2t/m3The moisture of the material cake is 5-15 wt%.
13. A process as claimed in claim 10, in which the cake has a density of from 1.1 to 1.5t/m 3The moisture of the material cake is 7-12 wt%.
14. The method of any one of claims 9-13, wherein in step (2), the heat treating comprises: a first stage, a second stage, a third stage, and a fourth stage.
15. The method of claim 14, wherein the first stage conditions comprise: the temperature is more than 100 ℃ and not more than 300 ℃; the time is 40-60 h.
16. The method of claim 14, wherein the first stage conditions comprise: the temperature is more than 150 ℃ and not more than 250 ℃; the time is 45-55 h.
17. The method of claim 14, wherein the second stage conditions comprise: the temperature is more than 300 ℃ and not more than 700 ℃; the time is 70-90 h.
18. The method of claim 14, wherein the second stage conditions comprise: the temperature is more than 400 ℃ and not more than 600 ℃; the time is 75-85 h.
19. The method of claim 14, wherein the third stage conditions comprise: the temperature is more than 700 ℃ and not more than 950 ℃, and the time is 30-50 h.
20. The method of claim 14, wherein the third stage conditions comprise: the temperature is more than 800 ℃ and not more than 950 ℃, and the time is 35-45 h.
21. The method of claim 14, wherein the fourth stage conditions comprise: the temperature is more than 950 ℃ and not more than 1500 ℃, and the time is 40-60 h.
22. The method of claim 14, wherein the fourth stage conditions comprise: the temperature is more than 950 ℃ and not more than 1350 ℃, and the time is 45-55 h.
23. Use of the carbon anode material precursor according to any one of claims 1 to 8, or the carbon anode material precursor obtained by the method according to any one of claims 9 to 22, in a carbon anode material.
24. A method of preparing a carbon anode material, the method comprising: the carbon negative electrode material precursor according to any one of claims 1 to 8 or the carbon negative electrode material precursor obtained by the method according to any one of claims 9 to 22 is graphitized to obtain a carbon negative electrode material.
25. The production method according to claim 24, wherein the conditions of the graphitization treatment include: the temperature is more than or equal to 2500 ℃, and the time is 10-60 h.
26. The production method according to claim 24, wherein the conditions of the graphitization treatment include: the temperature is 2500-.
27. A carbon negative electrode material produced by the method of any one of claims 24 to 26.
28. The carbon anode material according to claim 27, wherein parameters of the carbon anode material satisfy: the degree of graphitization is more than 90%, and the coefficient of thermal expansion is less than 1.7 multiplied by 105The porosity is more than 10% and the aperture ratio of less than 50nm is more than 40%.
29. A carbon negative electrode material produced by the method of any one of claims 24 to 26, or use of the carbon negative electrode material of claim 27 or 28 in a lithium ion battery.
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