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CN111171201A - Preparation method of carbon-chlorine high-molecular polymer intermediate and carbon-chlorine high-molecular polymer, carbon-chlorine high-molecular polymer and application thereof - Google Patents

Preparation method of carbon-chlorine high-molecular polymer intermediate and carbon-chlorine high-molecular polymer, carbon-chlorine high-molecular polymer and application thereof Download PDF

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CN111171201A
CN111171201A CN201911357533.4A CN201911357533A CN111171201A CN 111171201 A CN111171201 A CN 111171201A CN 201911357533 A CN201911357533 A CN 201911357533A CN 111171201 A CN111171201 A CN 111171201A
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carbon
molecular polymer
chlorine high
high molecular
chlorine
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王健
阎帅
吴江华
涂飞跃
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/14—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
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    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
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Abstract

The invention discloses a preparation method of a carbon-chlorine high molecular polymer intermediate, which comprises the following steps: (1) carrying out polymerization reaction on chlorinated olefin under the action of a catalyst to obtain a reactant; (2) and (2) centrifuging, washing and drying the reactant obtained in the step (1) to obtain the carbon-chlorine high molecular polymer intermediate. The invention also provides a preparation method of the carbon-chlorine high molecular polymer, which comprises the step of carbonizing the carbon-chlorine high molecular polymer intermediate in a protective atmosphere to obtain the carbon-chlorine high molecular polymer. The invention also provides a carbon-chlorine high molecular polymer obtained by the preparation method and application thereof. The carbon-chlorine high molecular polymer is used as a conductive agent, and the addition amount is small, and can reach about ten-thousandth of that of an active substance at least and is 1 percent of that of a conventional conductive agent.

Description

Preparation method of carbon-chlorine high-molecular polymer intermediate and carbon-chlorine high-molecular polymer, carbon-chlorine high-molecular polymer and application thereof
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a high-molecular polymer intermediate for electric conduction, a preparation method of a high-molecular polymer, the high-molecular polymer and application of the high-molecular polymer.
Background
With the increasing exhaustion of fossil energy such as petroleum and coal, the energy crisis and energy pollution approach to each other, and the acquisition of new energy has become urgent. The lithium ion battery has the advantages of high voltage, high energy density, high safety, low self-discharge rate and the like, and is a promising new energy product. With the further development of science and technology, people have higher and higher requirements on lithium ion batteries. In the application fields of electric vehicles, solar energy storage batteries, energy storage power stations, smart phones, portable computers and the like, the lithium ion batteries are required to have higher energy density.
The lithium ion battery mainly provides energy density by positive and negative active substances, and the conductive carbon is used as an indispensable conductive additive substance (namely a conductive agent) in the lithium ion battery, wherein the smaller the dosage of the conductive carbon is, the larger the proportion of the positive and negative active substances is, and the higher the energy density of the lithium ion battery is. The better the conductivity of the conductive agent, the less the amount of the conductive agent, and the more the proportion of the positive and negative electrode active materials. Therefore, the lithium ion battery conductive agent needs to have extremely excellent conductive performance, but the conductive performance of the conductive agent (such as the decimeter height SP) applied in the existing market is difficult to meet the requirement of low addition amount, and the energy density of the lithium ion battery is influenced by the addition amount of the conductive agent which is often large. The carbon-chlorine high molecular polymer is used as a high-performance carbide, and no report that the carbon-chlorine high molecular polymer is added as a conductive agent is found in the prior art, so that the carbon-chlorine high molecular polymer with more excellent performance is prepared and used as the conductive agent, and the addition amount of the conductive agent can be greatly reduced.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology, and provide a carbon-chlorine high-molecular polymer intermediate with excellent conductivity, a preparation method of the carbon-chlorine high-molecular polymer, the carbon-chlorine high-molecular polymer and application of the carbon-chlorine high-molecular polymer. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a carbon-chlorine high molecular polymer intermediate comprises the following steps:
(1) mixing organic solvent with chloro-olefin (C)mHnClk) Mixing, and carrying out polymerization reaction under the action of a catalyst to obtain a reactant; the organic solvent is a polar aprotic solvent, and the polar aprotic solvent is one or more of an ether, an amide, an amine, a sulfoxide, a ketone, a nitrile and an ester; the catalyst is a non-polar catalytic gas;
(2) and (2) centrifuging, washing and drying the reactant obtained in the step (1) to obtain the carbon-chlorine high molecular polymer intermediate.
In the above preparation method, preferably, the polar aprotic solvent is one or more of dimethyl sulfoxide, ethylene glycol dimethyl ether, dimethyl succinate, N-methylpyrrolidone and dimethylacetamide; the nonpolar catalytic gas is one or more of nitrogen, hydrogen and carbon dioxide (preferably with a purity of 99.9% or more). The carbon-chlorine high molecular polymer is synthesized under the condition of an organic non-aqueous solvent, has better lipophilicity and dispersion performance, and is uniformly dispersed by using small addition amount. The catalytic gas is required to be non-polar and to have a certain catalytic activity.
In the above preparation method, preferably, the mass ratio of the organic solvent to the chlorinated alkene is 10: (1-100). More preferably, the mass ratio of the polar aprotic solvent to the chlorinated alkene is 10: 1 the mass ratio is controlled mainly in consideration of the yield of the reaction product, and the yield of the reactants is affected by over-high or under-low mass ratio.
In the above preparation method, preferably, the chlorinated alkene is a linear chlorinated alkene, and the linear chlorinated alkene is one or more of tetrachloroethylene, hexachloropropene, pentachloropropene, tetrachloropropene, trichloropropene, dichloropropene, hexachlorobutadiene, pentachlorobutadiene, tetrachlorobutadiene, trichlorobutadiene, dichlorobutadiene and chloroprene. The use of linear chlorinated olefins facilitates polymerization, and the chlorinated olefins exemplified above are relatively less costly and more readily available as starting materials.
In the preparation method, the reaction temperature of the polymerization reaction is preferably 50-300 ℃, the reaction pressure is preferably 0-15MPa, and the reaction time is preferably 1-40 h. More preferably, the reaction temperature is 160 ℃, the reaction pressure is normal pressure, and the reaction time is 20 h. The above reaction temperature, reaction pressure and reaction time affect the molecular weight and yield of the polymer, and thus affect the properties such as specific surface area of the final carbonized product.
In the above production method, the reaction vessel at the time of polymerization reaction is preferably a ceramic vessel, a polytetrafluoroethylene vessel, a titanium steel vessel or a glass vessel.
In the above preparation method, preferably, the specific processes of centrifuging, washing and drying are as follows: centrifuging the reactant, removing the upper layer liquid, adding an ethanol solution, centrifuging, taking the precipitate, repeating for 3 times, and finally drying at 240 ℃ for 1h to obtain the carbon-chlorine high polymer intermediate.
In the preparation method, the polar aprotic solvent, the nonpolar catalytic gas and the linear chlorinated olefin are adopted to prepare the reactant through cross-linking polymerization reaction, the reactant is in a network structure, the subsequent resistant carbonization temperature is high, and the carbonization of the reactant into the carbon-chlorine high polymer is facilitated.
As a general technical concept, the invention also provides a preparation method of the carbon-chlorine high molecular polymer, wherein the carbon-chlorine high molecular polymer intermediate is carbonized in a tube furnace under protective atmosphere to obtain the carbon-chlorine high molecular polymer.
In the above preparation method, preferably, the carbonization treatment is carried out at 600 to 1300 ℃ for 0.5 to 4 hours. More preferably, the carbonization treatment is carried out at 1100-1200 ℃ for 0.5-4h, and still more preferably, the carbonization treatment is carried out at 1200 ℃ for 2 h. The carbonization temperature has great influence on the specific surface area and the conductivity of the carbon-chlorine high molecular polymer, hydrogen chloride or chlorine can be removed in the carbonization process to generate pores, the specific surface area of the material is increased, but the temperature is too high, the pore structure is unstable, and the pore structure collapse can be caused. And the carbonization temperature can influence the conductivity of the material, and at a proper carbonization temperature, the graphitization degree is good, the crystallinity of the material is good, the internal structure is tighter, the electron conduction is faster, and the conductivity is higher.
In the above production method, preferably, the protective atmosphere is argon gas. The density of the argon is higher than that of the nitrogen, so that the argon is more easily deposited in gaps at the bottom of the high molecular polymer, and the interference of other miscellaneous gases on the carbonization process is better and faster expelled.
As a general technical concept, the invention also provides a carbon-chlorine high molecular polymer obtained by the preparation method, wherein the conductivity of the carbon-chlorine high molecular polymer is 1800-3900S/m, and the specific surface area is 1600-2500m2/g。
As a general technical concept, the invention also provides an application of the carbon-chlorine high molecular polymer, wherein the carbon-chlorine high molecular polymer is used as a conductive agent of a battery electrode material, and the addition amount of the conductive agent is 0.005-0.015% of the mass of a positive electrode material. The conductive agent has higher conductivity, larger specific area and better dispersibility, can meet the requirement only by adopting 1 percent of the addition amount of the conventional conductive agent (the proportion of the conventional conductive agent is 0.5 to 1.5 percent), can increase the filling amount of the positive and negative electrode active substances, and has higher energy density.
In the above application, preferably, the positive electrode material is a ternary positive electrode material or lithium cobaltate. The research shows that the matching relationship between the carbon-chlorine high molecular polymer and the ternary cathode material or lithium cobaltate is good, and the addition amount of the conductive agent can be smaller.
The invention provides an application example of the carbon-chlorine high polymer as a conductive agent for preparing a lithium ion battery, wherein the lithium ion battery is a 18650 type cylindrical battery assembled by a positive electrode, a negative electrode, a diaphragm and electrolyte on a battery wire, wherein the positive electrode is made of a ternary material, the negative electrode is made of graphite, the diaphragm is made of celgard2400, and the electrolyte is commercial electrolyte KX 91793; the anode is prepared from a ternary material 532, a carbon-chlorine high polymer and polyvinylidene fluoride according to a mass ratio of 98.99: 0.01: 1, pressing into thin slices, and drying in vacuum at 80 ℃ for 12 h.
The principle of the invention is as follows: the invention takes chlorinated alkene as a carbon source, and the chlorinated alkene is polymerized under the action of a polar aprotic solvent and a nonpolar catalytic gas to prepare an asphalt phase polymer (intermediate), and then the asphalt phase polymer (intermediate) is carbonized at high temperature to obtain the carbon-chlorine polymer. The carbonization process can affect the conductivity and the specific surface area of the carbon-chlorine high molecular polymer, the conductivity and the specific surface area can be regulated and controlled by controlling the carbonization temperature, the carbon-chlorine high molecular polymer with high conductivity and large specific surface area is obtained, the addition amount of the carbon-chlorine high molecular polymer in the positive and negative active substances can be reduced, and the energy density of the positive and negative active substances is increased.
Compared with the prior art, the invention has the advantages that:
1. the preparation method provided by the invention is simple in process, convenient and fast to operate in the preparation process, low in raw material investment, low in equipment requirement and low in production investment.
2. The conductivity of the carbon-chlorine high molecular polymer reaches 103S/m, specific surface area of 5-2500m2The range of/g is adjustable, the specific surface area is large, and the dispersibility is good.
3. The carbon-chlorine high molecular polymer is used as a conductive agent, the addition amount is small, the addition amount can reach about ten-thousandth of that of an active substance at least, and is 1% of the dosage of a conventional conductive agent, compared with the conventional conductive agent material, the active substance proportion is fully improved and efficiently utilized, and the energy density and the cycle performance of a lithium ion battery can be greatly improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM photograph of a polymer obtained in example 17.
FIG. 2 is a diagram showing a distribution of specific surface area and pore size of a polymer obtained in example 17.
Fig. 3 is a graph of cycle data for a carbon chlorine high molecular polymer E, F, G, H and a commercial conductive agent (texas SP) after various carbonization temperatures.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1: reactant of carbon-chlorine high molecular polymer
200g of dimethyl sulfoxide is accurately weighed and added into a 1000mL glass reaction kettle, 20mL of tetrachloropropene is weighed by a measuring cylinder and slowly added into a three-port glass reaction container filled with an organic solvent, one port of the three-port glass reaction container is communicated with 99.9% nitrogen by volume fraction, the other two ports of the three-port glass reaction container are inserted into a condensation reflux pipe, and the temperature of an oil bath is raised to 160 ℃ for reaction for 1 h. After the reaction is finished, naturally cooling to room temperature, and collecting the obtained reactant.
Example 2: reactant of carbon-chlorine high molecular polymer
200g of ethylene glycol dimethyl ether is accurately weighed, added into a 1000mL glass reaction kettle, 20mL of tetrachloropropylene is weighed by a measuring cylinder, slowly added into a three-port glass reaction vessel containing an organic solvent, one port of the three-port glass reaction vessel is communicated with nitrogen with the volume fraction of 99.9%, the other two ports are inserted into a condensation reflux pipe, and the temperature of an oil bath is raised to 160 ℃ for reaction for 1 h. After the reaction is finished, naturally cooling to room temperature, and collecting the obtained reactant.
Example 3: reactant of carbon-chlorine high molecular polymer
200g of dimethyl succinate is accurately weighed and added into a 1000mL glass reaction kettle, 20mL of tetrachloropropene is weighed by a measuring cylinder and slowly added into a three-port glass reaction container filled with an organic solvent, wherein one port is communicated with 99.9% nitrogen by volume fraction, the other two ports are inserted into a condensation reflux pipe, and the oil bath is heated to 160 ℃ for reaction for 1 h. After the reaction is finished, naturally cooling to room temperature, and collecting the obtained reactant.
Example 4: reactant of carbon-chlorine high molecular polymer
200g of N-methylpyrrolidone is accurately weighed, the N-methylpyrrolidone is added into a 1000mL glass reaction kettle, 20mL of tetrachloropropene is weighed by a measuring cylinder, the tetrachloropropene is slowly added into three glass reaction containers filled with organic solvents, one opening is communicated with nitrogen with the volume fraction of 99.9%, the other two openings are inserted into a condensation reflux pipe, and the temperature of an oil bath is increased to 160 ℃ for reaction for 1 hour. After the reaction is finished, naturally cooling to room temperature, and collecting the obtained reactant.
Example 5: reactant of carbon-chlorine high molecular polymer
200g of dimethylacetamide is accurately weighed and added into a 1000mL glass reaction kettle, 20mL of tetrachloropropene is weighed by a measuring cylinder and slowly added into three glass reaction containers filled with organic solvents, wherein one opening is communicated with 99.9% nitrogen by volume fraction, the other two openings are inserted into a condensation reflux pipe, and the temperature is raised to 160 ℃ by oil bath for reaction for 1 h. After the reaction is finished, naturally cooling to room temperature, and collecting the obtained reactant.
Example 6: reactant of carbon-chlorine high molecular polymer
200g of ethylene glycol dimethyl ether is accurately weighed, added into a 1000mL glass reaction kettle, 200mL of tetrachloropropylene is measured by a measuring cylinder, slowly added into a three-port glass reaction vessel containing an organic solvent, one port of the three-port glass reaction vessel is communicated with 99.9% carbon dioxide by volume fraction, the other two ports are inserted into a condensation reflux pipe, and the temperature of an oil bath is raised to 160 ℃ for reaction for 1 h. After the reaction is finished, naturally cooling to room temperature, and collecting the obtained reactant.
Example 7: reactant of carbon-chlorine high molecular polymer
200g of ethylene glycol dimethyl ether is accurately weighed and added into a 1000mL glass reaction kettle, 200mL of tetrachloroethylene is measured by a measuring cylinder and slowly added into a three-port glass reaction vessel containing an organic solvent, wherein one port is communicated with 99.9% nitrogen by volume fraction, the other two ports are inserted into a condensation reflux pipe, and the oil bath is heated to 160 ℃ for reaction for 1 h. After the reaction is finished, naturally cooling to room temperature, and collecting the obtained reactant.
Example 8: reactant of carbon-chlorine high molecular polymer
200g of ethylene glycol dimethyl ether is accurately weighed and added into a 1000mL glass reaction kettle, 200mL of hexachlorobutadiene is measured by a measuring cylinder and slowly added into a three-port glass reaction vessel containing an organic solvent, wherein one port is communicated with 99.9% nitrogen by volume fraction, the other two ports are inserted into a condensation reflux pipe, and the temperature of an oil bath is raised to 160 ℃ for reaction for 1 h. After the reaction is finished, naturally cooling to room temperature, and collecting the obtained reactant.
Example 9: reactant of carbon-chlorine high molecular polymer
Accurately weighing 200g of ethylene glycol dimethyl ether, adding the ethylene glycol dimethyl ether into a 1000mL glass reaction kettle, measuring 200mL of trichloropropylene by using a measuring cylinder, slowly adding the trichloropropylene into a three-port glass reaction container filled with an organic solvent, wherein one port is communicated with 99.9% of nitrogen by volume fraction, the other two ports are inserted into a condensation reflux pipe, and heating the mixture in an oil bath to 160 ℃ for reaction for 1 h. After the reaction is finished, naturally cooling to room temperature, and collecting the obtained reactant.
Example 10: carbon-chlorine high molecular polymer intermediate
Collecting the reactant of the carbon-chlorine high molecular polymer in the example 7 into a 50mL centrifuge tube, centrifuging for 15 minutes at 8000r/min, sucking away the upper yellow liquid, adding 50% ethanol water solution into the centrifuge tube, repeating for 3 times, discarding the supernatant, collecting the solid product in the centrifuge tube, and drying in a vacuum oven at 80 ℃ for 5 hours to obtain the carbon-chlorine high molecular polymer intermediate.
Example 11: carbon-chlorine high molecular polymer
Under the protection of argon, the carbon-chlorine high molecular polymer intermediate obtained in the example 10 is subjected to tube furnace heat treatment at 600 ℃ for 120min, and a final product is collected to obtain a carbon-chlorine high molecular polymer A which is marked as CCl-600.
Example 12: carbon-chlorine high molecular polymer
Under the protection of argon, the carbon-chlorine high molecular polymer intermediate obtained in the example 10 is subjected to tube furnace heat treatment at 700 ℃ for 120min, and a final product is collected to obtain a carbon-chlorine high molecular polymer B, which is marked as CCl-700.
Example 13: carbon-chlorine high molecular polymer
Under the protection of argon, the carbon-chlorine high molecular polymer intermediate obtained in the example 10 is subjected to tube furnace heat treatment at 800 ℃ for 120min, and a final product is collected to obtain a carbon-chlorine high molecular polymer C which is marked as CCl-800.
Example 14: carbon-chlorine high molecular polymer
Under the protection of argon, the carbon-chlorine high molecular polymer intermediate obtained in the example 10 is subjected to tube furnace heat treatment at 900 ℃ for 120min, and a final product is collected to obtain a carbon-chlorine high molecular polymer D which is marked as CCl-900.
Example 15: carbon-chlorine high molecular polymer
Under the protection of argon, the carbon-chlorine high molecular polymer intermediate obtained in the example 10 is subjected to tube furnace heat treatment at 1000 ℃ for 120min, and a final product is collected to obtain a carbon-chlorine high molecular polymer E, which is marked as CCl-1000.
Example 16: carbon-chlorine high molecular polymer
Under the protection of argon, the carbon-chlorine high molecular polymer intermediate obtained in the example 10 is subjected to tube furnace heat treatment at 1100 ℃ for 120min, and a final product is collected to obtain a carbon-chlorine high molecular polymer F, which is marked as CCl-1100.
Example 17: carbon-chlorine high molecular polymer
Under the protection of argon, the carbon-chlorine high molecular polymer intermediate obtained in the example 10 is subjected to tube furnace heat treatment at 1200 ℃ for 120min, and a final product is collected to obtain a carbon-chlorine high molecular polymer G, which is marked as CCl-1200.
Example 18: carbon-chlorine high molecular polymer
Under the protection of argon, the carbon-chlorine high molecular polymer intermediate obtained in the example 10 is subjected to tube furnace heat treatment at 1300 ℃ for 120min, and a final product is collected to obtain a carbon-chlorine high molecular polymer H, which is marked as CCl-1300.
Example 19: carbon-chlorine high molecular polymer
Under the protection of nitrogen, the carbon-chlorine high molecular polymer intermediate obtained in the example 10 is subjected to tube furnace heat treatment at 800 ℃ for 120min, and the final product is collected to obtain the carbon-chlorine high molecular polymer I, which is marked as CCl-800N.
Example 20: carbon-chlorine high molecular polymer
Under the protection of nitrogen, the carbon-chlorine high molecular polymer intermediate obtained in the example 10 is subjected to tube furnace heat treatment at 900 ℃ for 120min, and a final product is collected to obtain a carbon-chlorine high molecular polymer J, which is marked as CCl-900N.
The carbon chlorine high molecular polymer materials A to J prepared in examples 11 to 20 were subjected to a carbon chlorine ratio test (carbon chlorine analyzer JN9918-9F), a specific surface area test (JB-1), and an electric conductivity test (FT-301), and the results are shown in Table 1 below.
Table 1: the mass percentage content, the specific surface area and the conductivity of carbon and chlorine in the carbon-chlorine high molecular polymer at different carbonization temperatures
Figure BDA0002336340090000071
FIG. 1 is an SEM image of the polymer obtained in example 17, which shows that the polymer in example 17 has a uniform particle size and a spherical morphology.
FIG. 2 is a graph showing the distribution of specific surface area and pore size of the polymer obtained in example 17, and it can be seen that the pore size of the polymer in example 17 is mainly distributed between 1 and 5 nm.
The carbon-chlorine high molecular polymers E (CCl-1000), F (CCl-1100) G (CCl-1200), H (CCl-1300) and the commercial conductive agent (SP with a height of kilometer) prepared in the examples 15 to 18 are taken as positive electrode conductive agent substances, fully mixed with the ternary positive electrode material 532 and PVDF respectively, and matched with graphite negative electrode plates with the same specification to assemble a 18650 type cylindrical battery through homogenizing, coating, rolling, slitting and tabletting. When the carbon-chlorine high polymer E, F, G, H is used as a conductive agent, the dosage of the ternary cathode material 532 is 989900g, the dosage of the carbon-chlorine high polymer E, F, G, H is 100g, and the dosage of PVDF is 10000 g. When the super-meter high SP is used as a conductive agent, the dosage of the ternary cathode material 532 is 980000g, the dosage of the super-meter high SP is 10000g, and the dosage of PVDF is 10000 g. The lithium ion battery charging and discharging performance test is carried out in a Xinwei battery tester CT-9000, the charging and discharging multiplying power is 2C, the cycle test is completed under the condition of room temperature of 25 ℃, and the result is shown in figure 3.
Fig. 3 is a graph of cycle data for a carbon chlorine high molecular polymer E, F, G, H and a commercial conductive agent (texas SP) after various carbonization temperatures. As can be seen from fig. 3, compared to the conventional high SP per decimeter, the carbon-chlorine high molecular polymer with 1% of the high SP per decimeter added as the conductive agent of the lithium ion secondary battery has very excellent cycle performance, wherein the cycle performance of the materials F (CCl-1100) and G (CCl-1200) is significantly better than that of the commercial conductive agent (high SP per decimeter). In addition, the amount of the positive electrode active material in the positive electrode material is significantly higher, and the energy density is relatively higher.

Claims (10)

1. A preparation method of a carbon-chlorine high molecular polymer intermediate is characterized by comprising the following steps:
(1) mixing an organic solvent with chlorinated olefin, and carrying out polymerization reaction under the action of a catalyst to obtain a reactant; the organic solvent is a polar aprotic solvent, and the polar aprotic solvent is one or more of an ether, an amide, an amine, a sulfoxide, a ketone, a nitrile and an ester; the catalyst is a non-polar catalytic gas;
(2) and (2) centrifuging, washing and drying the reactant obtained in the step (1) to obtain the carbon-chlorine high molecular polymer intermediate.
2. The method according to claim 1, wherein the polar aprotic solvent is one or more of dimethyl sulfoxide, ethylene glycol dimethyl ether, dimethyl succinate, N-methylpyrrolidone, and dimethylacetamide; the nonpolar catalytic gas is one or more of nitrogen, hydrogen and carbon dioxide; the mass ratio of the organic solvent to the chlorinated olefin is 10: (1-100).
3. The method of claim 1 or 2, wherein the chlorinated alkene is a linear chlorinated alkene that is one or more of tetrachloroethylene, hexachloropropene, pentachloropropene, tetrachloropropene, trichloropropene, dichloropropene, hexachlorobutadiene, pentachlorobutadiene, tetrachlorobutadiene, trichlorobutadiene, dichlorobutadiene, and monochlorobutadiene.
4. The process according to claim 1 or 2, wherein the polymerization is carried out at a reaction temperature of 50 to 300 ℃, a reaction pressure of 0 to 15MPa, and a reaction time of 1 to 40 hours.
5. A method for producing a polymer, characterized in that the polymer intermediate is carbonized in a protective atmosphere to obtain a polymer, wherein the intermediate is the polymer of the carbon-chlorine type according to any one of claims 1 to 4.
6. The method according to claim 5, wherein the carbonization treatment is a treatment at 600 to 1300 ℃ for 0.5 to 4 hours.
7. The method of claim 5 or 6, wherein the protective atmosphere is argon.
8. The polymer obtained by the method according to any one of claims 5 to 7, wherein the polymer has an electrical conductivity of 1800 to 3900S/m and a specific surface area of 1600 to 2500m2/g。
9. The use of a carbon-chlorine high-molecular polymer as claimed in claim 8, characterized in that the carbon-chlorine high-molecular polymer is used as a conductive agent of a battery electrode material, and the addition amount of the conductive agent is 0.005-0.015% of the mass of a positive electrode material.
10. Use according to claim 9, wherein the positive electrode material is a ternary positive electrode material or lithium cobaltate.
CN201911357533.4A 2019-12-25 2019-12-25 Preparation method of carbon-chlorine high-molecular polymer intermediate and carbon-chlorine high-molecular polymer, carbon-chlorine high-molecular polymer and application thereof Withdrawn CN111171201A (en)

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US3522228A (en) * 1966-05-19 1970-07-28 Sumitomo Chemical Co Novel method for polymerizing a vinyl compound in the presence of a carbon dioxide medium
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