CN108539181A - A kind of lithium-ion negative pole composite material and preparation method - Google Patents
A kind of lithium-ion negative pole composite material and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of lithium-ion negative pole composite material and preparation methods, including nucleome, it is coated on outside nucleome and has the middle layer of hole, is coated on the outer layer of middle layer, nucleome is nano-silicon, middle layer is to be compounded with the composite material of graphite, outer layer is amorphous carbon, the raw material of middle layer, including following raw material：Graphite, copper powder, maleic anhydride, rosin, methyltrimethoxysilane, polyvinyl alcohol, hydroxyethyl cellulose, carboxylic propyl methocel, 2 ethyl, 4 methylimidazole, polyvinylpyrrolidone, neopelex, polyethylene glycol, silane coupling agent KH 570, high tenacity modified additive；The lithium-ion negative pole composite material is then to coat amorphous carbon by preparing middle layer, taking up the ball the periphery that middle layer is coated on nucleome in the periphery of middle layer again, obtained after oversintering cools down.The lithium-ion negative pole composite material of the present invention has excellent toughness, and effectively increases service life.
Description
Technical field
The invention belongs to battery material preparing technical fields, and in particular to a kind of lithium-ion negative pole composite material and its preparation
Method.
Background technology
Lithium ion battery is a kind of secondary cell, it relies primarily on lithium ion battery, and movement carrys out work between a positive electrode and a negative electrode
Make, in charging process, Li+Round-trip insertion and deintercalation between two electrodes；When charging, Li+From positive deintercalation, by electrolysis
Matter is embedded in cathode, and cathode is in rich lithium state；It is then opposite when electric discharge.The development of lithium ion battery was derived from upper world's nineties, until
Modern only 20 years, the primary leap of lithium electricity industry at past 20 years, the attention with various countries to environment, new energy, lithium from
Sub- battery but will have the development advanced by leaps and bounds.
A kind of Chinese patent application document " composite cathode material of lithium ion battery and preparation method thereof（Application publication number：
CN107623116A）" disclose a kind of composite cathode material of lithium ion battery, including nucleome, be coated on outside the nucleome and
Middle layer with hole, the outer layer being coated on outside the middle layer, the nucleome are nano-silicon, and the middle layer is multiple
Closing has the oxidation Asia silicon of graphite, and the outer layer is amorphous carbon, and the battery cathode composite material is by changing preparation method
Into obtaining a kind of anode material of structure novel, cathode composite wood of the anode material in certain structure novel
Material, the anode material can control the volume expansion of silicon in certain space, effectively prevent the dusting of silicon electrode, improve
Cyclical stability can be used as the negative material of high-capacity lithium battery, and the preparation method is simple for process, be suitable for industrialized production.
A kind of Chinese patent literature " lithium ion battery silicon anode material and preparation method thereof（Authorization Notice No.：
CN106025243B）" a kind of lithium ion battery silicon anode material is disclosed, it is with sky to have double shell structurres, stratum nucleare
The composite Nano silicon materials of cavity configuration, hypostracum are carbon material clad, and outer shell is conducting polymer thin film, also discloses one
Nano-silicon and nanometer Fe_3O_4 microballoon are mixed carry out carbon coating first by the preparation method of kind composite cathode material of lithium ion battery,
Double shell structurres are formed, is to sacrifice template with nanometer Fe_3O_4 microballoon, Fe3O4 microballoons is sacrificed by etching agent, stratum nucleare is made to form tool
The composite Nano silicon materials for having cavity structure make stratum nucleare form the composite Nano silicon materials with cavity structure, effective to buffer
The volume expansion of nano material, the silicium cathode composite material have specific capacity high, cycle performance and high rate performance is excellent, vibration density
Spend the advantages that high.
Invention content
The object of the present invention is to provide a kind of lithium-ion negative pole composite material and preparation methods, to solve in Chinese patent
A kind of application documents " composite cathode material of lithium ion battery and preparation method thereof（Application publication number：CN107623116A）" and specially
A kind of sharp document " lithium ion battery silicon anode material and preparation method thereof（Authorization Notice No.：CN106025243B）" open
Composite cathode material of lithium ion battery on the basis of, how to optimize component, dosage, method etc., it is negative to improve the lithium ion battery
The problem of pole composite material toughness.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of lithium-ion negative pole composite material, including nucleome, be coated on outside the nucleome and with hole middle layer, be coated on
The outer layer of the middle layer, the nucleome are nano-silicon, and the middle layer is to be compounded with the composite material of graphite, the outer layer
For amorphous carbon；
The middle layer, including following raw material：Graphite, copper powder, maleic anhydride, rosin, methyltrimethoxysilane, polyethylene
Alcohol, hydroxyethyl cellulose, carboxylic propyl methocel, 2-ethyl-4-methylimidazole, polyvinylpyrrolidone, detergent alkylate
Sodium sulfonate, polyethylene glycol, Silane coupling reagent KH-570, high tenacity modified additive；
In the raw material of the middle layer, high tenacity modified additive, including following raw material：Carbon dust, wood fiber powder, bamboo fibre, steaming
Distilled water, ammonium persulfate, silane resin acceptor kh-550, vermiculite, antimony oxide, nano magnesia, ceramic powder, nanometer silicon carbide,
Potassium acetate, cetyl trimethylammonium bromide, octylisothiazolinone；
In the raw material of the middle layer, graphite, copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, silane coupling agent KH-
570, the weight ratio of high tenacity modified additive is（4-8）：（3-6）：（6-9）：（2-6）：（2-4）：（1-3）：（12-18）.
Further, in the raw material of the middle layer, graphite, copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, silicon
Alkane coupling agent kh-570, high tenacity modified additive weight ratio be 6：44.5：7.5：4：3：2：15.
Further, in the raw material of the middle layer, high tenacity modified additive, as unit of parts by weight, including following original
Material：10-20 parts of carbon dust, 5-15 parts of wood fiber powder, 4-8 parts of bamboo fibre, 16-36 parts of distilled water, 4-6 parts of ammonium persulfate, silane
2-5 parts of coupling agent KH-550,1-4 parts of vermiculite, 3-6 parts of antimony oxide, 2-5 parts of nano magnesia, 1-5 parts of ceramic powder, nanometer
4-8 parts of silicon carbide, 3-6 parts of potassium acetate, 2-8 parts of cetyl trimethylammonium bromide, 1-6 parts of octylisothiazolinone.
Further, in the raw material of the middle layer, high tenacity modified additive is prepared by following technique：It is protected in nitrogen
Under shield, carbon dust, wood fiber powder, bamboo fibre and distilled water are uniformly mixed, then heat to 80-90 DEG C, keeps the temperature 10-30min,
Then ammonium persulfate is added and silane resin acceptor kh-550 is uniformly mixed, 10-20min is stirred in 450-650r/min rotating speeds, it is cold
But material a is obtained to room temperature；Vermiculite, antimony oxide, nano magnesia, ceramic powder and nanometer silicon carbide are uniformly mixed, room
Temperature stands 2-6d, and potassium acetate, cetyl trimethylammonium bromide, octylisothiazolinone and material a is then added and is uniformly mixed,
1-3h is stirred in 1500-2500r/min rotating speeds, then heats to 100-120 DEG C, dry 2-5h obtains height after being cooled to room temperature
Toughness modified additive.
Further, the middle layer, as unit of parts by weight, including following raw material：4-8 parts of graphite, 3-6 parts of copper powder,
6-9 parts of maleic anhydride, 2-6 parts of rosin, 4-6 parts of methyltrimethoxysilane, 6-8 parts of polyvinyl alcohol, hydroxyethyl cellulose 3-5
Part, 2-6 parts of carboxylic propyl methocel, 1-5 parts of 2-ethyl-4-methylimidazole, 2-4 parts of polyvinylpyrrolidone, dodecyl
4-8 parts of benzene sulfonic acid sodium salt, 3-6 parts of polyethylene glycol, 1-3 parts of Silane coupling reagent KH-570,12-18 parts of high tenacity modified additive.
The present invention also provides a kind of preparation methods of lithium-ion negative pole composite material, include the following steps：
S1：At 70-90 DEG C, maleic anhydride and rosin are mixed, are warming up to 80-90 DEG C, 10-20in is kept the temperature, copper is then added
Powder, methyltrimethoxysilane, polyvinyl alcohol, hydroxyethyl cellulose, carboxylic propyl methocel, 2-ethyl-4-methylimidazole,
Polyvinylpyrrolidone, neopelex and polyethylene glycol are uniformly mixed, and are continuously heating to 120-140 DEG C, keep the temperature 15-
35min, the pH for then adjusting reaction system is 3-4, and reaction 3-5h is stood at 60-70 DEG C, is obtained containing midbody particle
Suspension；
S2：Graphite, Silane coupling reagent KH-570 and high tenacity modified additive are added in the suspension obtained into S1 to be uniformly mixed,
It is warming up to 80-90 DEG C, keeps the temperature 5-15min, 2-4h is stirred in 650-850r/min rotating speeds, is then spray-dried, in obtaining
Between material；
S3：The intermediate materials obtained in S2 are subjected to redox reaction under the protection of inert atmosphere, middle layer is prepared；
S4：The middle layer that S3 is obtained is coated on to the periphery of nucleome, then coats amorphous carbon in the periphery of middle layer again, in
10-20 minutes after 800-900 DEG C of sintering, it is cooled to room temperature to obtain lithium-ion negative pole composite material.
Further, in S2, the inlet temperature for controlling the spray drying is 210-320 DEG C, outlet temperature 80-
130℃。
Further, in S3, the temperature of redox reaction is 1300-1500 DEG C, and the time of redox reaction is 10-
15h。
The invention has the advantages that：
（1）By embodiment 1-3 and the data of comparative example 19 and comparative example 10 as it can be seen that lithium-ion negative pole made from embodiment 1-3
Toughness, porosity, capacitance and the cycle capacitance of composite material are all remarkably higher than made from comparative example 9 and comparative example 10
Toughness, porosity, capacitance and the cycle capacitance of lithium-ion negative pole composite material；It simultaneously can by the data of embodiment 1-3
See, embodiment 1 is optimum embodiment.
（2）By the data of comparative example 11-13 as it can be seen that graphite, copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, silicon
Alkane coupling agent kh-570, high tenacity modified additive weight ratio do not exist（4-8）：（3-6）：（6-9）：（2-6）：（2-4）：（1-3）：
（12-18）When in range, toughness, porosity, the capacitance of lithium-ion negative pole composite material obtained are opposite with cycle capacitance
The numerical value of the numerical value answered and embodiment 1-3 is very different, and the numerical value of embodiment 1-3 is much smaller than, with the prior art（9 He of comparative example
Comparative example 10）Numerical value it is suitable.Graphite of the present invention, copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, silane coupling agent
KH-570, high tenacity modified additive are as reinforcement system, by adding when embodiment 1-3 controls prepare lithium-ion negative pole composite material
Add the weight of graphite, copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, Silane coupling reagent KH-570, high tenacity modified additive
Measuring ratio is（4-8）：（3-6）：（6-9）：（2-6）：（2-4）：（1-3）：（12-18）, realize and utilize graphite copper in reinforcement system
Powder is as conductive material, using main component as major ingredient, and the intermediate materials of maleic anhydride and rosin as grafting is utilized, and
Using polyvinylpyrrolidone as the auxiliary agent of thickening, is acted on by the graft modification of Silane coupling reagent KH-570, utilize high tenacity
The excellent toughness of modified additive applies in the preparation of the lithium-ion negative pole composite material of the present invention, effectively increases the present invention
The service life and energization efficiency of lithium-ion negative pole composite material.
（3）High tenacity modified additive is by the way that under nitrogen protection, carbon dust, wood fiber powder, bamboo fibre and distilled water are mixed
It closes uniformly, then heats up, keep the temperature, ammonium persulfate is then added and silane resin acceptor kh-550 is uniformly mixed, stirring is cooled to room
Temperature obtains material a；Vermiculite, antimony oxide, nano magnesia, ceramic powder and nanometer silicon carbide are uniformly mixed, are stored at room temperature,
Then potassium acetate, cetyl trimethylammonium bromide, octylisothiazolinone and material a is added to be uniformly mixed, then stirring rises
Temperature, it is dry, it is obtained after being cooled to room temperature, using carbon dust, wood fiber powder, bamboo fibre as base-material, realizes conductive basis, and
Under the graft modification effect of initiator ammonium persulfate and graft modification auxiliary agent silane resin acceptor kh-550, realize leech
Stone, antimony oxide, nano magnesia, ceramic powder and nanometer silicon carbide equal strength toughness reinforced filling apply to the height of the present invention
In the preparation of toughness modified additive, base-material is grafted, and in potassium acetate, cetyl trimethylammonium bromide, octyl isothiazole
Under the strengthening action of the auxiliary materials such as quinoline ketone, the lithium-ion negative pole that the high tenacity modified additive that is prepared into applies to the present invention is compound
In the preparation of material, the excellent toughness of the lithium-ion negative pole composite material is effectively increased, and improve the lithium-ion negative pole
The service life of composite material, improves electrical efficiency.
（4）By embodiment 1 and the data of comparative example 1-9 as it can be seen that graphite, copper powder, maleic anhydride, rosin, polyvinyl pyrrole
Alkanone, Silane coupling reagent KH-570, high tenacity modified additive play synergistic effect in preparing lithium-ion negative pole composite material,
Collaboration improves toughness, porosity and the capacitance and cycle capacitance of the lithium-ion negative pole composite material；This is：Graphite,
Copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, Silane coupling reagent KH-570, high tenacity modified additive are as reinforcing body
System, wherein graphite and copper powder assign reinforcement system excellent electric conductivity as major ingredient, and maleic anhydride and rosin cooperation are used as and connect
Branch bonding auxiliary material so that under the bonding and reinforcing effect of polyvinylpyrrolidone, changed using the grafting of Silane coupling reagent KH-570
Property effect, realize high tenacity modified additive and be grafted to the conductive major ingredient outer surface that graphite and copper powder are constituted, apply to the present invention
Lithium-ion negative pole composite material preparation in, impart the present invention the excellent electric conductivity of lithium-ion negative pole composite material and
Toughness extends the service life and electrical efficiency of the lithium-ion negative pole composite material.
（5）The preparation method of the lithium-ion negative pole composite material of the present invention is simple, and by preparing suspension, stone is then added
After ink carries out graft modification, it is spray-dried to obtain intermediate materials, then carries out redox reaction, centre is prepared
Layer, middle layer are coated on the periphery of nucleome, then coat amorphous carbon in the periphery of middle layer again, sintering postcooling to room temperature obtains
To lithium-ion negative pole composite material, electrical efficiency, toughness and the service life of lithium-ion negative pole composite material are effectively increased.
Specific implementation mode
For ease of more fully understanding the present invention, it is illustrated by the following examples, these examples belong to the protection of the present invention
Range, but do not limit the scope of the invention.
In embodiment, the lithium-ion negative pole composite material, including nucleome, be coated on outside the nucleome and have hole
Middle layer, be coated on the outer layer of the middle layer, the nucleome is nano-silicon, and the middle layer is be compounded with graphite compound
Material, the outer layer are amorphous carbon；
The middle layer, as unit of parts by weight, including following raw material：4-8 parts of graphite, 3-6 parts of copper powder, 6-9 parts of maleic anhydride,
2-6 parts of rosin, 4-6 parts of methyltrimethoxysilane, 6-8 parts of polyvinyl alcohol, 3-5 parts of hydroxyethyl cellulose, carboxylic hydroxypropyl methyl are fine
It ties up 2-6 parts of element, 1-5 parts of 2-ethyl-4-methylimidazole, 2-4 parts of polyvinylpyrrolidone, 4-8 parts of neopelex, gather
3-6 parts of ethylene glycol, 1-3 parts of Silane coupling reagent KH-570,12-18 parts of high tenacity modified additive.
In the raw material of the middle layer, high tenacity modified additive is prepared by following technique：Under nitrogen protection, weight is pressed
10-20 parts of carbon dusts, 5-15 parts of wood fiber powders, 4-8 parts of bamboo fibres and 16-36 parts of distilled water are uniformly mixed by amount part, are then risen
Temperature keeps the temperature 10-30min to 80-90 DEG C, and 4-6 parts of ammonium persulfates are then added and 2-5 parts of silane resin acceptor kh-550 mixing are equal
It is even, 10-20min is stirred in 450-650r/min rotating speeds, is cooled to room temperature to obtain material a；1-4 parts of vermiculites, 3-6 parts three are aoxidized
Two antimony, 2-5 part nano magnesia, 1-5 parts of ceramic powders and 4-8 parts of nanometer silicon carbides are uniformly mixed, and are stored at room temperature 2-6d, are then added
Enter 3-6 parts of potassium acetates, 2-8 parts of cetyl trimethylammonium bromides, 1-6 parts of octylisothiazolinones and material a to be uniformly mixed, in
1500-2500r/min rotating speeds stir 1-3h, then heat to 100-120 DEG C, and dry 2-5h obtains high-ductility after being cooled to room temperature
Property modified additive.
The present invention also provides a kind of preparation methods of lithium-ion negative pole composite material, include the following steps：
S1：At 70-90 DEG C, maleic anhydride and rosin are mixed, are warming up to 80-90 DEG C, 10-20in is kept the temperature, copper is then added
Powder, methyltrimethoxysilane, polyvinyl alcohol, hydroxyethyl cellulose, carboxylic propyl methocel, 2-ethyl-4-methylimidazole,
Polyvinylpyrrolidone, neopelex and polyethylene glycol are uniformly mixed, and are continuously heating to 120-140 DEG C, keep the temperature 15-
35min, the pH for then adjusting reaction system is 3-4, and reaction 3-5h is stood at 60-70 DEG C, is obtained containing midbody particle
Suspension；
S2：Graphite, Silane coupling reagent KH-570 and high tenacity modified additive are added in the suspension obtained into S1 to be uniformly mixed,
It is warming up to 80-90 DEG C, keeps the temperature 5-15min, 2-4h is stirred in 650-850r/min rotating speeds, is then spray-dried, in obtaining
Between material, wherein control spray drying inlet temperature be 210-320 DEG C, outlet temperature be 80-130 DEG C；
S3：The intermediate materials obtained in S2 are subjected to redox reaction 10- under the protection of inert atmosphere in 1300-1500 DEG C
Middle layer is prepared in 15h；
S4：The middle layer that S3 is obtained is coated on to the periphery of nucleome, then coats amorphous carbon in the periphery of middle layer again, in
10-20 minutes after 800-900 DEG C of sintering, it is cooled to room temperature to obtain lithium-ion negative pole composite material.
Embodiment 1
A kind of lithium-ion negative pole composite material, including nucleome, be coated on outside the nucleome and with hole middle layer, be coated on
The outer layer of the middle layer, the nucleome are nano-silicon, and the middle layer is to be compounded with the composite material of graphite, the outer layer
For amorphous carbon；
The middle layer, as unit of parts by weight, including following raw material：6 parts of graphite, 4.5 parts of copper powder, 7.5 parts of maleic anhydride, pine
4 parts fragrant, 5 parts of methyltrimethoxysilane, 7 parts of polyvinyl alcohol, 4 parts of hydroxyethyl cellulose, 4 parts of carboxylic propyl methocel, 2-
3 parts of ethyl -4-methylimidazole, 3 parts of polyvinylpyrrolidone, 6 parts of neopelex, 4.5 parts of polyethylene glycol, silane are even
Join 2 parts of agent KH-570,15 parts of high tenacity modified additive.
In the raw material of the middle layer, high tenacity modified additive is prepared by following technique：Under nitrogen protection, weight is pressed
15 parts of carbon dusts, 10 parts of wood fiber powders, 6 parts of bamboo fibres and 26 parts of distilled water are uniformly mixed by amount part, then heat to 85 DEG C, are protected
Warm 20min, is then added 5 parts of ammonium persulfates and 3.5 parts of silane resin acceptor kh-550s are uniformly mixed, and is stirred in 550r/min rotating speeds
15min is cooled to room temperature to obtain material a；By 2.5 parts of vermiculites, 4.5 parts of antimony oxides, 3.5 parts of nano magnesias, 3 parts of ceramics
Powder and 6 parts of nanometer silicon carbides are uniformly mixed, and are stored at room temperature 4d, 4.5 parts of potassium acetates, 5 parts of cetyl trimethyl bromines are then added
Change ammonium, 3.5 parts of octylisothiazolinones and material a to be uniformly mixed, stirs 2h in 2000r/min rotating speeds, then heat to 110
DEG C, dry 3.5h obtains high tenacity modified additive after being cooled to room temperature.
The present invention also provides a kind of preparation methods of lithium-ion negative pole composite material, include the following steps：
S1：At 80 DEG C, maleic anhydride and rosin are mixed, are warming up to 85 DEG C, keeps the temperature 15in, copper powder, methyl three is then added
Methoxy silane, polyvinyl alcohol, hydroxyethyl cellulose, carboxylic propyl methocel, 2-ethyl-4-methylimidazole, polyethylene pyrrole
Pyrrolidone, neopelex and polyethylene glycol are uniformly mixed, and are continuously heating to 130 DEG C, are kept the temperature 25min, are then adjusted
The pH of reaction system is 3.5, and reaction 4h is stood at 65 DEG C, obtains the suspension containing midbody particle；
S2：Graphite, Silane coupling reagent KH-570 and high tenacity modified additive are added in the suspension obtained into S1 to be uniformly mixed,
85 DEG C are warming up to, 10min is kept the temperature, 3h is stirred in 750r/min rotating speeds, is then spray-dried, obtains intermediate materials, wherein
The inlet temperature of control spray drying is 265 DEG C, and outlet temperature is 105 DEG C；
S3：The intermediate materials obtained in S2 are subjected to redox reaction 13h in 1400 DEG C under the protection of inert atmosphere, are prepared
Obtain middle layer；
S4：The middle layer that S3 is obtained is coated on to the periphery of nucleome, then coats amorphous carbon in the periphery of middle layer again, in
15 minutes after 850 DEG C of sintering, it is cooled to room temperature to obtain lithium-ion negative pole composite material.
Embodiment 2
A kind of lithium-ion negative pole composite material, including nucleome, be coated on outside the nucleome and with hole middle layer, be coated on
The outer layer of the middle layer, the nucleome are nano-silicon, and the middle layer is to be compounded with the composite material of graphite, the outer layer
For amorphous carbon；
The middle layer, as unit of parts by weight, including following raw material：4 parts of graphite, 6 parts of copper powder, 6 parts of maleic anhydride, rosin 6
Part, 4 parts of methyltrimethoxysilane, 8 parts of polyvinyl alcohol, 3 parts of hydroxyethyl cellulose, 6 parts of carboxylic propyl methocel, 2- second
1 part of base -4-methylimidazole, 4 parts of polyvinylpyrrolidone, 4 parts of neopelex, 6 parts of polyethylene glycol, silane coupling agent
1 part of KH-570,18 parts of high tenacity modified additive.
In the raw material of the middle layer, high tenacity modified additive is prepared by following technique：Under nitrogen protection, weight is pressed
10 parts of carbon dusts, 15 parts of wood fiber powders, 4 parts of bamboo fibres and 36 parts of distilled water are uniformly mixed by amount part, then heat to 80 DEG C, are protected
Warm 30min, is then added 4 parts of ammonium persulfates and 5 parts of silane resin acceptor kh-550s are uniformly mixed, and is stirred in 450r/min rotating speeds
20min is cooled to room temperature to obtain material a；By 1 part of vermiculite, 6 parts of antimony oxides, 2 parts of nano magnesias, 5 parts of ceramic powders and 4
Part nanometer silicon carbide is uniformly mixed, and is stored at room temperature 6d, be then added 3 parts of potassium acetates, 8 parts of cetyl trimethylammonium bromides, 1 part
Octylisothiazolinone and material a are uniformly mixed, and are stirred 1h in 2500r/min rotating speeds, are then heated to 120 DEG C, and 2h is dried, cold
But to obtaining high tenacity modified additive after room temperature.
The present invention also provides a kind of preparation methods of lithium-ion negative pole composite material, include the following steps：
S1：At 70 DEG C, maleic anhydride and rosin are mixed, are warming up to 90 DEG C, keeps the temperature 10in, copper powder, methyl three is then added
Methoxy silane, polyvinyl alcohol, hydroxyethyl cellulose, carboxylic propyl methocel, 2-ethyl-4-methylimidazole, polyethylene pyrrole
Pyrrolidone, neopelex and polyethylene glycol are uniformly mixed, and are continuously heating to 140 DEG C, are kept the temperature 15min, are then adjusted
The pH of reaction system is 4, and reaction 5h is stood at 60 DEG C, obtains the suspension containing midbody particle；
S2：Graphite, Silane coupling reagent KH-570 and high tenacity modified additive are added in the suspension obtained into S1 to be uniformly mixed,
80 DEG C are warming up to, 15min is kept the temperature, 4h is stirred in 650r/min rotating speeds, is then spray-dried, obtains intermediate materials, wherein
The inlet temperature of control spray drying is 210 DEG C, and outlet temperature is 130 DEG C；
S3：The intermediate materials obtained in S2 are subjected to redox reaction 15h in 1300 DEG C under the protection of inert atmosphere, are prepared
Obtain middle layer；
S4：The middle layer that S3 is obtained is coated on to the periphery of nucleome, then coats amorphous carbon in the periphery of middle layer again, in
20 minutes after 800 DEG C of sintering, it is cooled to room temperature to obtain lithium-ion negative pole composite material.
Embodiment 3
A kind of lithium-ion negative pole composite material, including nucleome, be coated on outside the nucleome and with hole middle layer, be coated on
The outer layer of the middle layer, the nucleome are nano-silicon, and the middle layer is to be compounded with the composite material of graphite, the outer layer
For amorphous carbon；
The middle layer, as unit of parts by weight, including following raw material：8 parts of graphite, 3 parts of copper powder, 9 parts of maleic anhydride, rosin 2
Part, 6 parts of methyltrimethoxysilane, 6 parts of polyvinyl alcohol, 5 parts of hydroxyethyl cellulose, 2 parts of carboxylic propyl methocel, 2- second
5 parts of base -4-methylimidazole, 2 parts of polyvinylpyrrolidone, 8 parts of neopelex, 3 parts of polyethylene glycol, silane coupling agent
3 parts of KH-570,12 parts of high tenacity modified additive.
In the raw material of the middle layer, high tenacity modified additive is prepared by following technique：Under nitrogen protection, weight is pressed
20 parts of carbon dusts, 5 parts of wood fiber powders, 8 parts of bamboo fibres and 16 parts of distilled water are uniformly mixed by amount part, then heat to 90 DEG C, are protected
Warm 10min, is then added 6 parts of ammonium persulfates and 2 parts of silane resin acceptor kh-550s are uniformly mixed, and is stirred in 650r/min rotating speeds
10min is cooled to room temperature to obtain material a；By 4 parts of vermiculites, 3 parts of antimony oxides, 5 parts of nano magnesias, 1 part of ceramic powder and 8
Part nanometer silicon carbide is uniformly mixed, and is stored at room temperature 2d, be then added 6 parts of potassium acetates, 2 parts of cetyl trimethylammonium bromides, 6 parts
Octylisothiazolinone and material a are uniformly mixed, and are stirred 3h in 1500r/min rotating speeds, are then heated to 100 DEG C, and 5h is dried, cold
But to obtaining high tenacity modified additive after room temperature.
The present invention also provides a kind of preparation methods of lithium-ion negative pole composite material, include the following steps：
S1：At 90 DEG C, maleic anhydride and rosin are mixed, are warming up to 80 DEG C, keeps the temperature 20in, copper powder, methyl three is then added
Methoxy silane, polyvinyl alcohol, hydroxyethyl cellulose, carboxylic propyl methocel, 2-ethyl-4-methylimidazole, polyethylene pyrrole
Pyrrolidone, neopelex and polyethylene glycol are uniformly mixed, and are continuously heating to 120 DEG C, are kept the temperature 35min, are then adjusted
The pH of reaction system is 3, and reaction 3h is stood at 70 DEG C, obtains the suspension containing midbody particle；
S2：Graphite, Silane coupling reagent KH-570 and high tenacity modified additive are added in the suspension obtained into S1 to be uniformly mixed,
90 DEG C are warming up to, 5min is kept the temperature, 2h is stirred in 850r/min rotating speeds, is then spray-dried, obtains intermediate materials, wherein controlling
The inlet temperature of system spray drying is 320 DEG C, and outlet temperature is 80 DEG C；
S3：The intermediate materials obtained in S2 are subjected to redox reaction 10h in 1500 DEG C under the protection of inert atmosphere, are prepared
Obtain middle layer；
S4：The middle layer that S3 is obtained is coated on to the periphery of nucleome, then coats amorphous carbon in the periphery of middle layer again, in
10 minutes after 900 DEG C of sintering, it is cooled to room temperature to obtain lithium-ion negative pole composite material.
Comparative example 1
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that being lacked in the raw material of preparation lithium-ion negative pole composite material
Few graphite, copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, Silane coupling reagent KH-570, high tenacity modified additive.
Comparative example 2
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that being lacked in the raw material of preparation lithium-ion negative pole composite material
Few graphite.
Comparative example 3
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that being lacked in the raw material of preparation lithium-ion negative pole composite material
Few copper powder.
Comparative example 4
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that being lacked in the raw material of preparation lithium-ion negative pole composite material
Few maleic anhydride.
Comparative example 5
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that being lacked in the raw material of preparation lithium-ion negative pole composite material
Few rosin.
Comparative example 6
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that being lacked in the raw material of preparation lithium-ion negative pole composite material
Few polyvinylpyrrolidone.
Comparative example 7
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that being lacked in the raw material of preparation lithium-ion negative pole composite material
Few Silane coupling reagent KH-570.
Comparative example 8
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that being lacked in the raw material of preparation lithium-ion negative pole composite material
Few high tenacity modified additive.
Comparative example 9
Using a kind of Chinese patent application document " composite cathode material of lithium ion battery and preparation method thereof（Application publication number：
CN107623116A）" in method described in specific embodiment 1-5 prepare composite cathode material of lithium ion battery.
Comparative example 10
Using a kind of Chinese patent literature " lithium ion battery silicon anode material and preparation method thereof（Authorization Notice No.：
CN106025243B）" in method described in specific embodiment 1-4 prepare composite cathode material of lithium ion battery.
Comparative example 11
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare lithium-ion negative pole composite material raw material in stone
Ink is 3 parts, copper powder is 7 parts, maleic anhydride is 5 parts, 7 parts of rosin, 1 part of polyvinylpyrrolidone, Silane coupling reagent KH-570 4
Part, high tenacity modified additive are 11 parts.
Comparative example 12
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare lithium-ion negative pole composite material raw material in stone
Ink is 9 parts, copper powder is 2 parts, maleic anhydride is 11 parts, 8 parts of rosin, 1 part of polyvinylpyrrolidone, Silane coupling reagent KH-570 are
5 parts, high tenacity modified additive be 10 parts.
Comparative example 13
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare lithium-ion negative pole composite material raw material in stone
Ink is 10 parts, copper powder is 2 parts, maleic anhydride is 11 parts, 0.6 part of rosin, 6 parts of polyvinylpyrrolidone, silane coupling agent KH-
570 be 5 parts, high tenacity modified additive is 10 parts.
Toughness, porosity and capacitance test are carried out to product made from embodiment 1-3 and comparative example 1-13, as a result such as
Shown in following table.
As seen from the above table：（1）By embodiment 1-3 and the data of comparative example 19 and comparative example 10 as it can be seen that embodiment 1-3 systems
The toughness of lithium-ion negative pole composite material, porosity, capacitance and cycle capacitance be all remarkably higher than comparative example 9 and
The toughness, porosity of lithium-ion negative pole composite material made from comparative example 10, capacitance and cycle capacitance；Simultaneously by implementing
The data of example 1-3 are as it can be seen that embodiment 1 is optimum embodiment.
（2）By embodiment 1 and the data of comparative example 1-9 as it can be seen that graphite, copper powder, maleic anhydride, rosin, polyvinyl pyrrole
Alkanone, Silane coupling reagent KH-570, high tenacity modified additive play synergistic effect in preparing lithium-ion negative pole composite material,
Collaboration improves toughness, porosity and the capacitance and cycle capacitance of the lithium-ion negative pole composite material；This is：Graphite,
Copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, Silane coupling reagent KH-570, high tenacity modified additive are as reinforcing body
System, wherein graphite and copper powder assign reinforcement system excellent electric conductivity as major ingredient, and maleic anhydride and rosin cooperation are used as and connect
Branch bonding auxiliary material so that under the bonding and reinforcing effect of polyvinylpyrrolidone, changed using the grafting of Silane coupling reagent KH-570
Property effect, realize high tenacity modified additive and be grafted to the conductive major ingredient outer surface that graphite and copper powder are constituted, apply to the present invention
Lithium-ion negative pole composite material preparation in, impart the present invention the excellent electric conductivity of lithium-ion negative pole composite material and
Toughness extends the service life and electrical efficiency of the lithium-ion negative pole composite material.
Wherein, high tenacity modified additive is by under nitrogen protection, by carbon dust, wood fiber powder, bamboo fibre and distilled water
It is uniformly mixed, then heats up, keep the temperature, ammonium persulfate is then added and silane resin acceptor kh-550 is uniformly mixed, stirring is cooled to
Room temperature obtains material a；Vermiculite, antimony oxide, nano magnesia, ceramic powder and nanometer silicon carbide are uniformly mixed, room temperature is quiet
It sets, potassium acetate, cetyl trimethylammonium bromide, octylisothiazolinone and material a is then added and is uniformly mixed, stirring, so
After heat up, it is dry, obtained after being cooled to room temperature, base-material be used as using carbon dust, wood fiber powder, bamboo fibre, realizes the base of conduction
Plinth, and under the graft modification of initiator ammonium persulfate and graft modification auxiliary agent silane resin acceptor kh-550 effect, realize
Vermiculite, antimony oxide, nano magnesia, ceramic powder and nanometer silicon carbide equal strength toughness reinforced filling are applied into the present invention
High tenacity modified additive preparation in, base-material is grafted, and different in potassium acetate, cetyl trimethylammonium bromide, octyl
Under the strengthening action of the auxiliary materials such as thiazolinone, the high tenacity modified additive being prepared into applies to the lithium-ion negative pole of the present invention
In the preparation of composite material, the excellent toughness of the lithium-ion negative pole composite material is effectively increased, and improve the lithium ion
The service life of anode material, improves electrical efficiency.
（3）By the data of comparative example 11-13 as it can be seen that graphite, copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, silicon
Alkane coupling agent kh-570, high tenacity modified additive weight ratio do not exist（4-8）：（3-6）：（6-9）：（2-6）：（2-4）：（1-3）：
（12-18）When in range, toughness, porosity, the capacitance of lithium-ion negative pole composite material obtained are opposite with cycle capacitance
The numerical value of the numerical value answered and embodiment 1-3 is very different, and the numerical value of embodiment 1-3 is much smaller than, with the prior art（9 He of comparative example
Comparative example 10）Numerical value it is suitable.Graphite of the present invention, copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, silane coupling agent
KH-570, high tenacity modified additive are as reinforcement system, by adding when embodiment 1-3 controls prepare lithium-ion negative pole composite material
Add the weight of graphite, copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, Silane coupling reagent KH-570, high tenacity modified additive
Measuring ratio is（4-8）：（3-6）：（6-9）：（2-6）：（2-4）：（1-3）：（12-18）, realize and utilize graphite copper in reinforcement system
Powder is as conductive material, using main component as major ingredient, and the intermediate materials of maleic anhydride and rosin as grafting is utilized, and
Using polyvinylpyrrolidone as the auxiliary agent of thickening, is acted on by the graft modification of Silane coupling reagent KH-570, utilize high tenacity
The excellent toughness of modified additive applies in the preparation of the lithium-ion negative pole composite material of the present invention, effectively increases the present invention
The service life and energization efficiency of lithium-ion negative pole composite material.
The above content is it cannot be assumed that present invention specific implementation is confined to these explanations, for the technical field of the invention
Those of ordinary skill for, under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all answers
When being considered as belonging to present invention scope of patent protection determined by the appended claims.
Claims (8)
1. a kind of lithium-ion negative pole composite material, which is characterized in that including nucleome, be coated on outside the nucleome and there is hole
Middle layer, the outer layer for being coated on the middle layer, the nucleome are nano-silicon, and the middle layer is to be compounded with the composite wood of graphite
Material, the outer layer are amorphous carbon；
The raw material of the middle layer, including following raw material：Graphite, maleic anhydride, rosin, methyltrimethoxysilane, gathers copper powder
Vinyl alcohol, hydroxyethyl cellulose, carboxylic propyl methocel, 2-ethyl-4-methylimidazole, polyvinylpyrrolidone, dodecane
Base benzene sulfonic acid sodium salt, polyethylene glycol, Silane coupling reagent KH-570, high tenacity modified additive；
In the raw material of the middle layer, high tenacity modified additive, including following raw material：Carbon dust, wood fiber powder, bamboo fibre, steaming
Distilled water, ammonium persulfate, silane resin acceptor kh-550, vermiculite, antimony oxide, nano magnesia, ceramic powder, nanometer silicon carbide,
Potassium acetate, cetyl trimethylammonium bromide, octylisothiazolinone；
In the raw material of the middle layer, graphite, copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, silane coupling agent KH-
570, the weight ratio of high tenacity modified additive is（4-8）：（3-6）：（6-9）：（2-6）：（2-4）：（1-3）：（12-18）.
2. lithium-ion negative pole composite material according to claim 1, which is characterized in that in the raw material of the middle layer, stone
The weight ratio of ink, copper powder, maleic anhydride, rosin, polyvinylpyrrolidone, Silane coupling reagent KH-570, high tenacity modified additive
It is 6：44.5：7.5：4：3：2：15.
3. lithium-ion negative pole composite material according to claim 1, which is characterized in that high in the raw material of the middle layer
Toughness modified additive, as unit of parts by weight, including following raw material：10-20 parts of carbon dust, 5-15 parts of wood fiber powder, bamboo fibre
4-8 parts, 16-36 parts of distilled water, 4-6 parts of ammonium persulfate, 2-5 parts of silane resin acceptor kh-550,1-4 parts of vermiculite, antimony oxide
3-6 parts, 2-5 parts of nano magnesia, 1-5 parts of ceramic powder, 4-8 parts of nanometer silicon carbide, 3-6 parts of potassium acetate, cetyl trimethyl
2-8 parts of ammonium bromide, 1-6 parts of octylisothiazolinone.
4. lithium-ion negative pole composite material according to claim 1, which is characterized in that high in the raw material of the middle layer
Toughness modified additive is prepared by following technique：Under nitrogen protection, by carbon dust, wood fiber powder, bamboo fibre and distilled water
It is uniformly mixed, then heats to 80-90 DEG C, keep the temperature 10-30min, ammonium persulfate is then added and silane resin acceptor kh-550 is mixed
It closes uniformly, stirs 10-20min in 450-650r/min rotating speeds, be cooled to room temperature to obtain material a；By vermiculite, antimony oxide,
Nano magnesia, ceramic powder and nanometer silicon carbide are uniformly mixed, and are stored at room temperature 2-6d, and potassium acetate, cetyl three is then added
Methyl bromide ammonium, octylisothiazolinone and material a are uniformly mixed, and are stirred 1-3h in 1500-2500r/min rotating speeds, are then risen
For temperature to 100-120 DEG C, dry 2-5h obtains high tenacity modified additive after being cooled to room temperature.
5. lithium-ion negative pole composite material according to claim 1, which is characterized in that as unit of parts by weight, including with
Lower raw material：4-8 parts of graphite, 3-6 parts of copper powder, 6-9 parts of maleic anhydride, 2-6 parts of rosin, 4-6 parts of methyltrimethoxysilane, poly- second
6-8 parts of enol, 3-5 parts of hydroxyethyl cellulose, 2-6 parts of carboxylic propyl methocel, 1-5 parts of 2-ethyl-4-methylimidazole, poly- second
2-4 parts of alkene pyrrolidone, 4-8 parts of neopelex, 3-6 parts of polyethylene glycol, 1-3 parts of Silane coupling reagent KH-570, height
12-18 parts of toughness modified additive.
6. a kind of preparation method according to claim 1-5 any one of them lithium-ion negative pole composite materials, which is characterized in that
Include the following steps：
S1：At 70-90 DEG C, maleic anhydride and rosin are mixed, are warming up to 80-90 DEG C, 10-20in is kept the temperature, copper is then added
Powder, methyltrimethoxysilane, polyvinyl alcohol, hydroxyethyl cellulose, carboxylic propyl methocel, 2-ethyl-4-methylimidazole,
Polyvinylpyrrolidone, neopelex and polyethylene glycol are uniformly mixed, and are continuously heating to 120-140 DEG C, keep the temperature 15-
35min, the pH for then adjusting reaction system is 3-4, and reaction 3-5h is stood at 60-70 DEG C, is obtained containing midbody particle
Suspension；
S2：Graphite, Silane coupling reagent KH-570 and high tenacity modified additive are added in the suspension obtained into S1 to be uniformly mixed,
It is warming up to 80-90 DEG C, keeps the temperature 5-15min, 2-4h is stirred in 650-850r/min rotating speeds, is then spray-dried, in obtaining
Between material；
S3：The intermediate materials obtained in S2 are subjected to redox reaction under the protection of inert atmosphere, middle layer is prepared；
S4：The middle layer that S3 is obtained is coated on to the periphery of nucleome, then coats amorphous carbon in the periphery of middle layer again, in
10-20 minutes after 800-900 DEG C of sintering, it is cooled to room temperature to obtain lithium-ion negative pole composite material.
7. the preparation method of lithium-ion negative pole composite material according to claim 6, which is characterized in that in S2, control institute
The inlet temperature for the spray drying stated is 210-320 DEG C, and outlet temperature is 80-130 DEG C.
8. the preparation method of lithium-ion negative pole composite material according to claim 6, which is characterized in that in S3, oxidation is also
The temperature of original reaction is 1300-1500 DEG C, and the time of redox reaction is 10-15h.
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