CN102881869A - Modified hard carbon negative electrode material for lithium ion battery and preparation method for modified hard carbon negative electrode material - Google Patents
Modified hard carbon negative electrode material for lithium ion battery and preparation method for modified hard carbon negative electrode material Download PDFInfo
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Abstract
The invention discloses a modified hard carbon negative electrode material for a lithium ion battery and a preparation method for the modified hard carbon negative electrode material. The preparation method is simple and feasible, the modified hard carbon negative electrode material can be prepared through uniform mixing, pyrolysis, coating and the like, the production cost is low and the preparation method can be applied to industrial production. The modified hard carbon negative electrode material has high electrochemical properties and high lithium intercalating and separating capacity, has the first discharge specific capacity of more than 926 mAh/g, and has the first discharge specific capacity of 982 mAh/g and the first charge discharge efficiency of 93 percent in the optimal mode of execution, and is suitable for power and energy storage lithium ion batteries.
Description
Technical field
The present invention relates to a kind of battery material and preparation method thereof, relate in particular to modification hard carbon cathode material that a kind of lithium ion battery uses and preparation method thereof.
Background technology
The electrokinetic cell that uses at present mainly contains lead-acid battery, Ni-MH battery, nickel-cadmium cell, lithium ion battery, and along with the day by day enhancing of people's environmental consciousness, the use of the battery of the toxic metals such as leaded, cadmium is restricted day by day.Since nineteen ninety, lithium ion battery was by develop, to compare other traditional battery because of it and have preferably chemical property, its range of application is more and more extensive.And mostly prior art is that adopting the graphite of graphite or modification is the negative material of lithium ion battery, and graphite material is because degree of graphitization is high, and the layer structure with height causes embedding lithium capacity lower.And hard carbon is the lithium ion battery of negative material, receives much concern owing to the special structure of its hard carbon cathode material makes it preferably the use under high current charge-discharge.Sony company has at first developed and has used hard carbon that poly furfuryl alcohol PFA thermal cracking makes as the lithium ion battery of negative material, but its specific capacity and efficiency for charge-discharge are still lower, and can not satisfy now people have the demand of more excellent chemical property to battery.
Summary of the invention
The object of the invention is to for overcoming the defective of prior art, and provide that a kind of lithium ion battery is used and have high power capacity and the modification hard carbon cathode material of high charge-discharge efficient and preparation method thereof.
For achieving the above object, the present invention by the following technical solutions: the modification hard carbon cathode material that a kind of lithium ion battery is used comprises hard carbon matrix, additive and coating; Described hard carbon matrix predecessor comprise in phenolic resins, Merlon, epoxy resin, acrylic resin, polyvinyl chloride and the polyformaldehyde any one or multiple, the composition of hard carbon matrix predecessor is preferably by phenolic resins and Merlon and forms, and the mass ratio of phenolic resins and Merlon is 2:1-1.5; Described additive comprises crystalline graphite powder and boron phosphate, the D50 of crystalline graphite powder≤5 μ m, the quality of crystalline flake graphite and boron phosphate is respectively 0.5-5% and the 0.1-0.5% of hard carbon matrix predecessor, and the quality of crystalline flake graphite and boron phosphate is preferably respectively 2% and 0.2% of hard carbon matrix predecessor; Described coating comprises carboxymethyl cellulose, polyphenylene sulfide, Kynoar, furane resins, the ethyl-methyl carbonic ester, polyvinyl alcohol, polystyrene, polymethyl-benzene olefin(e) acid methyl esters, polytetrafluoroethylene, polyacrylonitrile, polyethylene, poly(ethylene oxide), PPOX, polyethylene glycol succinate, poly-SA ethylene glycol, the polyethylene glycol imines, polyacetylene, polyaniline, polypyrrole, poly-acene, polythiophene, poly m-phenylene diamine, polyimides, PVP, pitch; one or more in the butadiene-styrene rubber; the quality of coating is the 1-15% of hard carbon substrate quality; the quality optimization of coating is 12% of hard carbon substrate quality; the composition of coating is preferably by carboxymethyl cellulose; Kynoar and polyphenylene sulfide form, carboxymethyl cellulose; the mass ratio of Kynoar and polyphenylene sulfide is 4:1-2:1-1.5.
The preparation method of the modification hard carbon cathode material that a kind of lithium ion battery is used may further comprise the steps:
(1) in isopropyl alcohol, adds hard carbon matrix predecessor, crystalline graphite powder and boron phosphate, stir, place 30-60min under the normal temperature, then under 45 ℃, dry and naturally cool to room temperature, then at room temperature solidify 1-50h, be preferably 35h curing time, obtain solid precursor;
(2) under the protection of nitrogen or inert gas, step (1) gained solid precursor is warming up to 400 ℃ with the programming rate of 2-5 ℃/min, insulation 1h, then the programming rate with 0.1-3 ℃/min is warming up to 500-1500 ℃, then insulation 2-24h naturally cools to room temperature, obtains hard carbon;
(3) hard carbon is carried out ball milling or pulverizing, obtaining granularity is the hard carbon matrix of 1-60 μ m;
(4) in the hard carbon matrix, add coating; mix; rotating speed is 500-3500r/min, and the time is 15-120min, then under the protection of nitrogen or inert gas; programming rate with 0.1-10 ℃/min is warming up to 500-1000 ℃; naturally cool to 200 ℃, then continue to be warming up to 800-1500 ℃ with the programming rate of 0.1-10 ℃/min, insulation 2-10h; temperature retention time is preferably 7h, naturally is cooled to room temperature.
Compared with prior art, the invention has the beneficial effects as follows: modification hard carbon cathode material of the present invention has good chemical property, have good embedding lithium, take off the lithium ability, first discharge specific capacity is all more than 926mAh/g, in the best execution mode, first discharge specific capacity is up to 982mAh/g, and first charge-discharge efficiency is applicable to power and energy storage lithium ion battery up to 93%; Preparation method of the present invention is simple and easy to do, and cost is low, can be applicable to suitability for industrialized production.
Embodiment
In order to more fully understand technology contents of the present invention, below in conjunction with specific embodiment technical scheme of the present invention is further introduced and explanation.
The modification hard carbon cathode material that a kind of lithium ion battery is used comprises hard carbon matrix, additive and coating; Described hard carbon matrix predecessor comprise in phenolic resins, Merlon, epoxy resin, acrylic resin, polyvinyl chloride and the polyformaldehyde any one or multiple; Described additive comprises crystalline graphite powder and boron phosphate, the D50 of crystalline graphite powder≤5 μ m, and the quality of crystalline flake graphite and boron phosphate is respectively 0.5-5% and the 0.1-0.5% of hard carbon matrix predecessor; Described coating comprises carboxymethyl cellulose, polyphenylene sulfide, Kynoar, furane resins, the ethyl-methyl carbonic ester, polyvinyl alcohol, polystyrene, polymethyl-benzene olefin(e) acid methyl esters, polytetrafluoroethylene, polyacrylonitrile, polyethylene, poly(ethylene oxide), PPOX, polyethylene glycol succinate, poly-SA ethylene glycol, the polyethylene glycol imines, polyacetylene, polyaniline, polypyrrole, poly-acene, polythiophene, poly m-phenylene diamine, polyimides, PVP, pitch; one or more in the butadiene-styrene rubber, the quality of coating are the 1-15% of hard carbon substrate quality.
Embodiment 1
In the 0.5L isopropyl alcohol, add 60g phenolic resins, 40g Merlon, 2g crystalline graphite powder and 0.2g boron phosphate, with machine mixer stir and normal temperature under place 50min, then under 45 ℃, dry and naturally cool to room temperature, then at room temperature solidify 35h, obtain solid precursor; Solid precursor places resistance furnace, under the nitrogen protection, is warming up to 400 ℃ with the programming rate of 2 ℃/min, insulation 1h, and then the programming rate with 1 ℃/min is warming up to 1200 ℃, and then insulation 15h naturally cools to room temperature, obtains hard carbon; With hard carbon ball milling or pulverizing 60min, obtaining granularity is the hard carbon matrix of 50 μ m with ball mill; Take by weighing above-mentioned gained hard carbon matrix 100g and 5.7g carboxymethyl cellulose, 2.8g Kynoar, 1.5g polyphenylene sulfide; be put in the mixer and mix; rotating speed is 2500r/min; time is 90min, then under nitrogen protection, is warming up to 800 ℃ with the programming rate of 0.5 ℃/min; naturally cool to 200 ℃; then continue to be warming up to 1500 ℃ with the programming rate of 5 ℃/min, insulation 7h naturally is cooled to room temperature at last and obtains the modification hard carbon cathode material.
Embodiment 2
In the 0.5L isopropyl alcohol, add 60g phenolic resins, 40g Merlon, 2g crystalline graphite powder and 0.2g boron phosphate, with machine mixer stir and normal temperature under place 60min, then under 45 ℃, dry and naturally cool to room temperature, then at room temperature solidify 50h, obtain solid precursor; Solid precursor places resistance furnace, under the nitrogen protection, is warming up to 400 ℃ with the programming rate of 3 ℃/min, insulation 1h, and then the programming rate with 3 ℃/min is warming up to 1500 ℃, and then insulation 24h naturally cools to room temperature, obtains hard carbon; With hard carbon ball milling or pulverizing 60min, obtaining granularity is the hard carbon matrix of 50 μ m with ball mill; Take by weighing above-mentioned gained hard carbon matrix 100g and 5.7g carboxymethyl cellulose, 2.8g Kynoar, 1.5g polyphenylene sulfide; be put in the mixer and mix; rotating speed is 3500r/min; time is 120min, then under nitrogen protection, is warming up to 1000 ℃ with the programming rate of 5 ℃/min; naturally cool to 200 ℃; then continue to be warming up to 1500 ℃ with the programming rate of 0.1 ℃/min, insulation 10h naturally is cooled to room temperature at last and obtains the modification hard carbon cathode material.
Embodiment 3
In the 0.5L isopropyl alcohol, add 60g phenolic resins, 40g Merlon, 2g crystalline graphite powder and 0.2g boron phosphate, with machine mixer stir and normal temperature under place 30min, then under 45 ℃, dry and naturally cool to room temperature, then at room temperature solidify 1h, obtain solid precursor; Solid precursor places resistance furnace, under the nitrogen protection, is warming up to 400 ℃ with the programming rate of 5 ℃/min, insulation 1h, and then the programming rate with 3 ℃/min is warming up to 800 ℃, and then insulation 2h naturally cools to room temperature, obtains hard carbon; With hard carbon ball milling or pulverizing 60min, obtaining granularity is the hard carbon matrix of 50 μ m with ball mill; Take by weighing above-mentioned gained hard carbon matrix 100g and 5.7g carboxymethyl cellulose, 2.8g Kynoar, 1.5g polyphenylene sulfide; be put in the mixer and mix; rotating speed is 500r/min; time is 15min, then under nitrogen protection, is warming up to 800 ℃ with the programming rate of 10 ℃/min; naturally cool to 200 ℃; then continue to be warming up to 1500 ℃ with the programming rate of 10 ℃/min, insulation 2h naturally is cooled to room temperature at last and obtains the modification hard carbon cathode material.
Embodiment 4
In the 0.5L isopropyl alcohol, add 60g phenolic resins, 45g Merlon, 2.1g crystalline graphite powder and 0.21g boron phosphate, with machine mixer stir and normal temperature under place 50min, then under 45 ℃, dry and naturally cool to room temperature, then at room temperature solidify 35h, obtain solid precursor; Solid precursor places resistance furnace, under the nitrogen protection, is warming up to 400 ℃ with the programming rate of 2 ℃/min, insulation 1h, and then the programming rate with 1 ℃/min is warming up to 1200 ℃, and then insulation 15h naturally cools to room temperature, obtains hard carbon; With hard carbon ball milling or pulverizing 60min, obtaining granularity is the hard carbon matrix of 50 μ m with ball mill; Take by weighing above-mentioned gained hard carbon matrix 100g and 9.6g carboxymethyl cellulose, 2.4g Kynoar, 2.9g polyphenylene sulfide; be put in the mixer and mix; rotating speed is 2500r/min; time is 90min, then under nitrogen protection, is warming up to 800 ℃ with the programming rate of 0.5 ℃/min; naturally cool to 200 ℃; then continue to be warming up to 1500 ℃ with the programming rate of 5 ℃/min, insulation 7h naturally is cooled to room temperature at last and obtains the modification hard carbon cathode material.
Embodiment 5
In the 0.5L isopropyl alcohol, add 60g phenolic resins, 30g Merlon, 2g crystalline graphite powder and 0.2g boron phosphate, with machine mixer stir and normal temperature under place 50min, then under 45 ℃, dry and naturally cool to room temperature, then at room temperature solidify 35h, obtain solid precursor; Solid precursor places resistance furnace, under the nitrogen protection, is warming up to 400 ℃ with the programming rate of 2 ℃/min, insulation 1h, and then the programming rate with 1 ℃/min is warming up to 1200 ℃, and then insulation 15h naturally cools to room temperature, obtains hard carbon; With hard carbon ball milling or pulverizing 60min, obtaining granularity is the hard carbon matrix of 50 μ m with ball mill; Take by weighing above-mentioned gained hard carbon matrix 100g and 0.57g carboxymethyl cellulose, 0.21g Kynoar, 0.21g polyphenylene sulfide; be put in the mixer and mix; rotating speed is 2500r/min; time is 90min, then under nitrogen protection, is warming up to 800 ℃ with the programming rate of 0.5 ℃/min; naturally cool to 200 ℃; then continue to be warming up to 1500 ℃ with the programming rate of 5 ℃/min, insulation 7h naturally is cooled to room temperature at last and obtains the modification hard carbon cathode material.
Embodiment 6
In the 0.5L isopropyl alcohol, add 100g phenolic resins, 5g crystalline graphite powder and 0.5g boron phosphate, with machine mixer stir and normal temperature under place 60min, then under 45 ℃, dry and naturally cool to room temperature, then at room temperature solidify 50h, obtain solid precursor; Solid precursor places resistance furnace, and neon protection is lower, is warming up to 400 ℃ with the programming rate of 2 ℃/min, insulation 1h, and then the programming rate with 1 ℃/min is warming up to 1200 ℃, and then insulation 24h naturally cools to room temperature, obtains hard carbon; With hard carbon ball milling or pulverizing 60min, obtaining granularity is the hard carbon matrix of 60 μ m with ball mill; Take by weighing above-mentioned gained hard carbon matrix 100g and 9g polythiophene, 5g polymethyl-benzene olefin(e) acid methyl esters; be put in the mixer and mix; rotating speed is 2500r/min; time is 120min, then under neon protection, is warming up to 500 ℃ with the programming rate of 0.5 ℃/min; naturally cool to 200 ℃; then continue to be warming up to 1500 ℃ with the programming rate of 5 ℃/min, insulation 5h naturally is cooled to room temperature at last and obtains the modification hard carbon cathode material.
Embodiment 7
In the 0.5L isopropyl alcohol, add 100g Merlon, 2g crystalline graphite powder and 0.2g boron phosphate, with machine mixer stir and normal temperature under place 40min, then under 45 ℃, dry and naturally cool to room temperature, then at room temperature solidify 50h, obtain solid precursor; Solid precursor places resistance furnace, under the argon shield, is warming up to 400 ℃ with the programming rate of 2 ℃/min, insulation 1h, and then the programming rate with 1 ℃/min is warming up to 1200 ℃, and then insulation 15h naturally cools to room temperature, obtains hard carbon; With hard carbon ball milling or pulverizing 60min, obtaining granularity is the hard carbon matrix of 45 μ m with ball mill; Take by weighing above-mentioned gained hard carbon matrix 100g and 12g poly(ethylene oxide); be put in the mixer and mix; rotating speed is 2500r/min; time is 90min, then under argon shield, is warming up to 800 ℃ with the programming rate of 0.5 ℃/min; naturally cool to 200 ℃; then continue to be warming up to 1500 ℃ with the programming rate of 5 ℃/min, insulation 10h naturally is cooled to room temperature at last and obtains the modification hard carbon cathode material.
Embodiment 8
In the 0.5L isopropyl alcohol, add 45g phenolic resins, 30g epoxy resin, 25 acrylic resins, 5g crystalline graphite powder and 0.5g boron phosphate, with machine mixer stir and normal temperature under place 50min, then under 45 ℃, dry and naturally cool to room temperature, then at room temperature solidify 35h, obtain solid precursor; Solid precursor places resistance furnace, under the nitrogen protection, is warming up to 400 ℃ with the programming rate of 2 ℃/min, insulation 1h, and then the programming rate with 1 ℃/min is warming up to 1200 ℃, and then insulation 15h naturally cools to room temperature, obtains hard carbon; With hard carbon ball milling or pulverizing 60min, obtaining granularity is the hard carbon matrix of 50 μ m with ball mill; Take by weighing above-mentioned gained hard carbon matrix 100g and 5g furane resins, 2g PPOX, 1g polystyrene, the poly-SA ethylene glycol of 1g; be put in the mixer and mix; rotating speed is 2500r/min; time is 90min, then under nitrogen protection, is warming up to 800 ℃ with the programming rate of 0.5 ℃/min; naturally cool to 200 ℃; then continue to be warming up to 1500 ℃ with the programming rate of 5 ℃/min, insulation 7h naturally is cooled to room temperature at last and obtains the modification hard carbon cathode material.
Embodiment 9
In the 0.5L isopropyl alcohol, add 50g polyvinyl chloride, 50g polyformaldehyde, 0.5g crystalline graphite powder and 0.1g boron phosphate, with machine mixer stir and normal temperature under place 50min, then under 45 ℃, dry and naturally cool to room temperature, then at room temperature solidify 35h, obtain solid precursor; Solid precursor places resistance furnace, under the argon shield, is warming up to 400 ℃ with the programming rate of 2 ℃/min, insulation 1h, and then the programming rate with 1 ℃/min is warming up to 1000 ℃, and then insulation 15h naturally cools to room temperature, obtains hard carbon; With hard carbon ball milling or pulverizing 60min, obtaining granularity is the hard carbon matrix of 50 μ m with ball mill; Take by weighing above-mentioned gained hard carbon matrix 100g and 10g polyethylene glycol imines, 3g polyaniline; be put in the mixer and mix; rotating speed is 3500r/min; time is 90min, then under argon shield, is warming up to 800 ℃ with the programming rate of 0.5 ℃/min; naturally cool to 200 ℃; then continue to be warming up to 1300 ℃ with the programming rate of 5 ℃/min, insulation 5h naturally is cooled to room temperature at last and obtains the modification hard carbon cathode material.
Electrochemical property test
The chemical property of test modification hard carbon cathode material, the half-cell method of testing is: modification hard carbon cathode material sample, the 1-METHYLPYRROLIDONE that contains the 6-7% Kynoar and conductive black mix in the ratio of 91.6:6.6:1.8, be applied on the Copper Foil, it is that 110 ℃ of dry 4h of vacuum drying chamber are for subsequent use that the pole piece that coats is put into temperature.Simulated battery is assemblied in the glove box that is full of argon gas and carries out, and electrolyte is 1mol/L LiPF
6+ EC:DEC:DMC=1:1:1(volume ratio), metal lithium sheet is to electrode.This simulated battery is mainly used in testing its initial charge specific capacity, first discharge specific capacity and first charge-discharge efficiency, and the chemical property of having tested two kinds of native graphites processing without the inventive method is as Comparative Examples.The test of specific capacity electric current with 0.1C on battery testing system is discharged to 2.5V with simulated battery first from 0.005V, record discharge capacity, the quality of specific capacity=discharge capacity/negative material; First charge-discharge efficiency test constant current with 0.5mA on battery testing system charges to 0.005V with above-mentioned simulated battery, then with the constant current of 0.2mA with battery discharge to 2.5V, record first discharge capacity and initial charge capacity, discharge capacity/initial charge capacity * 100% of first charge-discharge efficiency=first.Test result is as shown in the table.
Test data in the upper table shows, the first charge-discharge efficiency of modification hard carbon cathode material of the present invention is generally higher, and the embedding lithium of modification hard carbon cathode material, to take off the lithium performance good.
The above only further specifies technology contents of the present invention with embodiment, so that the reader is more readily understood, does not only limit to this but do not represent embodiments of the present invention, and any technology of doing according to the present invention is extended or recreation, all is subjected to protection of the present invention.
Claims (8)
1. modification hard carbon cathode material that lithium ion battery is used, it is characterized in that: the modification hard carbon cathode material that described lithium ion battery is used comprises hard carbon matrix, additive and coating; Described hard carbon matrix predecessor comprises phenolic resins, Merlon, epoxy resin, acrylic resin, in polyvinyl chloride and the polyformaldehyde any one or multiple, described additive comprises crystalline graphite powder and boron phosphate, and described coating comprises carboxymethyl cellulose, polyphenylene sulfide, Kynoar, furane resins, the ethyl-methyl carbonic ester, polyvinyl alcohol, polystyrene, polymethyl-benzene olefin(e) acid methyl esters, polytetrafluoroethylene, polyacrylonitrile, polyethylene, poly(ethylene oxide), PPOX, polyethylene glycol succinate, poly-SA ethylene glycol, the polyethylene glycol imines, polyacetylene, polyaniline, polypyrrole, poly-acene, polythiophene, poly m-phenylene diamine, polyimides, PVP, pitch; one or more in the butadiene-styrene rubber.
2. the modification hard carbon cathode material used of described a kind of lithium ion battery according to claim 1, it is characterized in that, the quality of described crystalline flake graphite and boron phosphate is respectively 0.5-5% and the 0.1-0.5% of hard carbon matrix predecessor, the D50 of crystalline graphite powder≤5 μ m, the quality of described coating is the 1-15% of hard carbon substrate quality.
3. the modification hard carbon cathode material used of described a kind of lithium ion battery according to claim 1 is characterized in that, the quality of described crystalline flake graphite and boron phosphate is respectively 2% and 0.2% of hard carbon matrix predecessor, and the quality of described coating is 12% of hard carbon substrate quality.
4. the modification hard carbon cathode material used of described a kind of lithium ion battery according to claim 1 is characterized in that, described hard carbon matrix predecessor is comprised of phenolic resins and Merlon, and the mass ratio of phenolic resins and Merlon is 2:1-1.5.
5. the modification hard carbon cathode material used of described a kind of lithium ion battery according to claim 1, it is characterized in that, described coating is comprised of carboxymethyl cellulose, Kynoar and polyphenylene sulfide, and the mass ratio of carboxymethyl cellulose, Kynoar and polyphenylene sulfide is 4:1-2:1-1.5.
6. the preparation method of the modification hard carbon cathode material used of a lithium ion battery is characterized in that may further comprise the steps:
(1) in isopropyl alcohol, adds hard carbon matrix predecessor, crystalline graphite powder and boron phosphate, stir, place 30-60min under the normal temperature, and then dry and naturally cool to room temperature under 45 ℃, then at room temperature solidify 1-50h, obtain solid precursor;
(2) under the protection of nitrogen or inert gas, step (1) gained solid precursor is warming up to 400 ℃ with the programming rate of 2-5 ℃/min, insulation 1h, then the programming rate with 0.1-3 ℃/min is warming up to 500-1500 ℃, then insulation 2-24h naturally cools to room temperature, obtains hard carbon;
(3) hard carbon is carried out ball milling or pulverizing, obtaining granularity is the hard carbon matrix of 1-60 μ m;
(4) in the hard carbon matrix, add coating; mix; rotating speed is 500-3500r/min; time is 15-120min, then under the protection of nitrogen or inert gas, is warming up to 500-1000 ℃ with the programming rate of 0.1-10 ℃/min; naturally cool to 200 ℃; then continue to be warming up to 800-1500 ℃ with the programming rate of 0.1-10 ℃/min, insulation 2-10h is cooled to room temperature naturally.
7. the preparation method of the modification hard carbon cathode material used of described a kind of lithium ion battery according to claim 6 is characterized in that, be 35h the curing time of described step (1).
8. the preparation method of the modification hard carbon cathode material used of described a kind of lithium ion battery according to claim 6 is characterized in that, the temperature retention time of described step (4) is 7h.
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