CN103346293B - Lithium ion battery cathode material and its preparation method, lithium ion battery - Google Patents

Lithium ion battery cathode material and its preparation method, lithium ion battery Download PDF

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CN103346293B
CN103346293B CN201310272311.9A CN201310272311A CN103346293B CN 103346293 B CN103346293 B CN 103346293B CN 201310272311 A CN201310272311 A CN 201310272311A CN 103346293 B CN103346293 B CN 103346293B
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lithium ion
ion battery
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preparation
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CN103346293A (en
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裴晓英
李志虎
夏永高
刘兆平
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NINGBO FULI BATTERY MATERIAL TECHNOLOGY CO., LTD.
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Ningbo Institute of Material Technology and Engineering of CAS
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    • Y02E60/10Energy storage using batteries

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Abstract

The invention provides a kind of lithium ion battery cathode material and its preparation method, lithium ion battery, this lithium ion battery negative material comprises kernel, is wrapped in the intermediate layer of described kernel outside and the shell be wrapped in outside described intermediate layer, described kernel is silicon carbide particles, intermediate layer is carbon foam layer, and shell is amorphous carbon layer; Described silicon carbide particles is formed by silicon grain and material with carbon element.Compared with prior art, the present invention comprises intermediate layer carbon foam layer between silicon carbide particles kernel and amorphous carbon shell, first carbon foam layer can form conductive grid structure, can not only improve the electric conductivity of material, also silicon grain enormousness change in available buffer charge and discharge process; Secondly, outer shell amorphous carbon layer can maintain the nucleocapsid structure of negative material, the coating layer also available buffer change in volume of nucleocapsid structure, improve the cyclical stability of electrode, reduce the contact of active material and electrolyte, improve the coulombic efficiency first of electrode, also can stop nanoparticle agglomerates, improve electrode conductivuty.

Description

Lithium ion battery cathode material and its preparation method, lithium ion battery
Technical field
The invention belongs to technical field of electrochemistry, particularly relate to lithium ion battery cathode material and its preparation method, lithium ion battery.
Background technology
Lithium ion battery has that operating voltage is high, specific energy is high, operating temperature range is wide, electric discharge is steady, volume is little, quality is light, memory-less effect and the advantage such as environmentally friendly, therefore illustrates wide application prospect in fields such as portable electric appts, electric automobile, space technology, national defense industry.And, along with mobile electronic equipment to high power capacity, long-life batteries demand growing, the performance of people to lithium ion battery is had higher requirement, and negative material is as the key factor improving lithium ion battery energy and cycle life, worldwide obtains and study widely.
At the beginning of the end of the year in 20th century 90, Sony corporation of Japan will take the lead in developing carbon negative pole material, significantly improve security performance and the charge and discharge circulation life of lithium ion battery.But, the theoretical specific capacity of carbon negative pole material only has 372mAh/g, its energy density cannot meet present various electronic equipment for consumption, and especially energy storage device and electric motor car are to the requirement of energy density, therefore in the urgent need to finding a kind of negative material that can replace the high-energy-density of material with carbon element.
Wherein, silicon based anode material is with its huge lithium storage content (4200mAh/g), receive much concern a little more than advantages such as the discharge platform of material with carbon element and the rich reserves in the earth's crust.But in charge and discharge process, the reaction of the removal lithium embedded of silicon by with 310% change in volume, very easily cause coming off of the cracking of electrode and active material, thus cause the deterioration of electrode cycle performance.
For the serious bulk effect of silicon materials, modification need be carried out to improve cycle performance to it, one of them effective method prepares Si-C composite material exactly, make it have nucleocapsid structure, namely at Surface coating one deck carbon simple substance of silicon grain, the efflorescence of silicon grain can be suppressed like this to avoid again contingent silicon grain agglomeration in charge and discharge process.
Publication number is that the Chinese patent of 101339987A discloses a kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof, it passes through silica flour and graphite mixing and ball milling, and then add pitch or polymer overmold material ball milling again, carbonization treatment, carries out shattering, sieving acquisition composite negative pole material.This composite negative pole material is a kind of nucleocapsid structure, and in material, the content range of elemental silicon is 0.01 ~ 10%, and carbon content scope is 90 ~ 99.9%.The shortcoming of Si-C composite material to existing silicon-carbon cathode material cycle performance difference that this kind of method obtains has some improvement, but the structure comparison of outer field amorphous carbon layer is closely knit, in charge and discharge process, because the enormousness of silicon changes, easy to crack, efflorescence, causes electrode cycle degradation, and after 0.5C discharge and recharge, 50 circulations, the conservation rate of capacity is only 63%, high rate performance is poor, needs to be improved further.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide lithium ion battery cathode material and its preparation method, lithium ion battery, and this negative material cycle performance is better.
The invention provides a kind of lithium ion battery negative material, comprise kernel, be wrapped in the intermediate layer of described kernel outside and be wrapped in the shell of outside, described intermediate layer, described kernel is silicon carbide particles, and described intermediate layer is carbon foam layer, and described shell is amorphous carbon layer; Described silicon carbide particles is formed by silicon grain and material with carbon element.
Preferably, the thickness in described intermediate layer is 50 ~ 100nm.
Preferably, the thickness of described shell is 1 ~ 10 μm.
Preferably, the particle diameter of described lithium ion battery negative material is 10 ~ 50 μm.
Preferably, described material with carbon element is selected from one or more in native graphite, Delanium, celion, petroleum coke, needle coke, carbon fiber, MCMB and carbon nano-tube.
Present invention also offers a kind of preparation method of lithium ion battery negative material, comprise the following steps:
A) by silica flour and material with carbon element mixing and ball milling, the first mixture is obtained;
B) described first mixture, the first carbon encapsulated material are mixed with blowing agent, ball milling, obtain the second mixture;
C) mixed with the second carbon encapsulated material by described second mixture, ball milling, then roasting under inert gas shielding, obtains lithium ion battery negative material.
Preferably, described first carbon encapsulated material and the second carbon encapsulated material are selected from one or more in glucose, sucrose, citric acid, phenolic resins, petroleum asphalt, benzene naphthalene dicarboxylic copolymer, epoxy resin, carboxymethyl cellulose, polyacrylonitrile, polyvinyl alcohol and polystyrene independently of one another.
Preferably, described first carbon encapsulated material and the second carbon encapsulated material also comprise one or more in Graphene, carbon nano-tube, carbon fiber, carbon black independently of one another.
Preferably, described blowing agent is selected from one or more in azodiisobutyronitrile, Celogen Az, benzene sulfonyl hydrazide, unifor, benzene diazonium aminobenzene and urea.
Preferably, the quality of described blowing agent is 0.1% ~ 20% of the first mixture quality.
Preferably, the mass ratio of described first carbon encapsulated material and the first mixture is (1 ~ 10): (1 ~ 5).
Preferably, the mass ratio of described second carbon encapsulated material and the second mixture is (5 ~ 20): (1 ~ 5).
Present invention also offers a kind of lithium ion battery, comprise lithium ion battery negative material.
The invention provides a kind of lithium ion battery cathode material and its preparation method, lithium ion battery, this lithium ion battery negative material comprises kernel, is wrapped in the intermediate layer of described kernel outside and the shell be wrapped in outside described intermediate layer, described kernel is silicon carbide particles, intermediate layer is carbon foam layer, and shell is amorphous carbon layer; Described silicon carbide particles is formed by silicon grain and material with carbon element.Compared with the silicon-carbon composite cathode material of prior art nucleocapsid structure, the present invention comprises intermediate layer carbon foam layer between silicon carbide particles kernel and amorphous carbon shell, first carbon foam layer can form conductive grid structure, this structure can not only improve the electric conductivity of material, and in available buffer charge and discharge process, the enormousness of silicon grain changes; Secondly, outer shell amorphous carbon layer can maintain the nucleocapsid structure of negative material further, the coating layer available buffer change in volume of nucleocapsid structure, reduce stress, improve the cyclical stability of electrode, reduce the contact of active material and electrolyte, improve the coulombic efficiency first of electrode, also can stop nanoparticle agglomerates, improve electrode conductivuty, therefore the present invention is combined by carbon foam layer and amorphous carbon layer, and the cyclical stability of lithium ion battery negative material and high rate performance are improved further.
Accompanying drawing explanation
Fig. 1 is the structural representation of lithium ion battery negative material of the present invention;
Fig. 2 is that the lithium ion battery negative material obtained by the embodiment of the present invention 1 prepares battery and the lithium ion battery negative material that obtained by embodiment 2 prepares the charging and discharging curve of battery;
Fig. 3 is the rate charge-discharge curve that the lithium ion battery negative material obtained by the embodiment of the present invention 1 prepares battery.
Embodiment
The invention provides a kind of lithium ion battery negative material, comprise kernel, be wrapped in the intermediate layer of described kernel outside and be wrapped in the shell of outside, described intermediate layer, described kernel is silicon carbide particles, and intermediate layer is carbon foam layer, and shell is amorphous carbon layer; Described silicon carbide particles is formed by silicon grain and material with carbon element.As shown in Figure 1, wherein 1 is shell amorphous carbon layer to its schematic diagram, and 2 and 3 is silicon carbide particles, and 2 is material with carbon element, and 3 is silicon grain, and 4 is intermediate layer carbon foam layer.
Wherein, the particle diameter of lithium ion battery negative material of the present invention is 10 ~ 50 μm, is preferably 15 ~ 40 μm; In this negative material, the content of silicon is preferably 10 ~ 50wt%, is more preferably 20 ~ 40wt%, and carbon content is preferably 50 ~ 90wt%, is more preferably 60 ~ 80wt%.
Silicon carbide particles is the kernel of lithium ion battery negative material of the present invention, carbonaceous negative material change in volume in charge and discharge process is relatively little, there is good stable circulation performance, and good conductivity, and the chemical property of silicon and carbon is close, the two can be combined closely, and the basis material (i.e. dispersible carrier) therefore using material with carbon element as dispersed silicon particle, using silicon carbide particles as the inner nuclear material of negative material.Described material with carbon element is material with carbon element well known to those skilled in the art, there is no special restriction, in the present invention, be preferably one or more in native graphite, Delanium, celion, petroleum coke, needle coke, carbon fiber, MCMB and carbon nano-tube.
The intermediate layer of described lithium ion battery negative material is carbon foam layer, and its thickness is 50 ~ 100nm, is preferably 60 ~ 80nm.Carbon foam layer can form conductive grid structure on the one hand, and improve the electric conductivity of negative material, on the other hand, this structure can give the space of change in volume, effectively cushions the enormousness change of silicon grain in charge and discharge process.
Amorphous carbon layer forms the shell of lithium ion battery negative material of the present invention, and its thickness is 1 ~ 10 μm, is preferably 3 ~ 8 μm.Amorphous carbon layer is the amorphous carbon layer forming nucleocapsid structure shell in lithium ion battery negative material well known to those skilled in the art, there is no special restriction.Amorphous carbon layer can maintain the nucleocapsid structure of negative material further, the coating layer available buffer change in volume of nucleocapsid structure, reduce stress, improve the cyclical stability of electrode, reduce the contact of active material and electrolyte, improve the coulombic efficiency first of electrode, also can stop nanoparticle agglomerates, improve electrode conductivuty.
The change in volume space of the present invention by utilizing carbon foam layer to improve material, and the nucleocapsid structure of amorphous carbon layer immobilization material, make the cyclical stability of lithium ion battery negative material and high rate performance be further improved.
Present invention also offers the preparation method of above-mentioned lithium ion battery negative material, comprise the following steps: a) by silica flour and material with carbon element mixing and ball milling, obtain the first mixture; B) described first mixture, the first carbon encapsulated material are mixed with blowing agent, ball milling, obtain the second mixture; C) mixed with the second carbon encapsulated material by described second mixture, ball milling, then roasting under inert gas shielding, obtains lithium ion battery negative material.
Wherein, by silica flour and material with carbon element mixing and ball milling, obtain the first mixture, this mixture is the kernel silicon carbide particles of lithium ion battery negative material.Described silica flour is silica flour well known to those skilled in the art, there is no special restriction, for making silicon grain be nano-dispersed between material with carbon element, is preferably nano silica fume; Described material with carbon element is same as above, does not repeat them here; The mass ratio of described silica flour and material with carbon element is (1 ~ 5): (1 ~ 10), is preferably (2 ~ 4): (3 ~ 7); Described step a) in the method for ball milling be those skilled in the art's well-known process, there is no special restriction, in order to ball milling evenly, preferably adopt wet ball grinding; The medium of described wet ball grinding is preferably absolute ethyl alcohol, anhydrous propanone or anhydrous carbon tetrachloride; The rotating speed of described ball milling is preferably 300 ~ 600rmp, is more preferably 300 ~ 500rmp; The time of described ball milling is preferably 5 ~ 10h, is more preferably 6 ~ 8h.
In the first mixture, add the first carbon encapsulated material and blowing agent, mixing and ball milling, obtain the second mixture.Wherein, after preferred ball milling through spraying dry.Wherein, described first carbon encapsulated material is well known to those skilled in the artly can be used for coated material with carbon element, there is no special restriction, in the present invention, be preferably one or more in glucose, sucrose, citric acid, phenolic resins, petroleum asphalt, benzene naphthalene dicarboxylic copolymer, epoxy resin, carboxymethyl cellulose, polyacrylonitrile, polyvinyl alcohol and polystyrene; The mass ratio of described first carbon encapsulated material and the first mixture is preferably (1 ~ 10): (1 ~ 5), is more preferably (1 ~ 6): (1 ~ 2); Described blowing agent is blowing agent well known to those skilled in the art, there is no special restriction, is preferably one or more in azodiisobutyronitrile, Celogen Az, benzene sulfonyl hydrazide, unifor, benzene diazonium aminobenzene and urea; The quality of described blowing agent is 0.1% ~ 20% of the first mixture quality, is preferably 1% ~ 15%.
In the present invention, in the first mixture, add the first carbon encapsulated material and blowing agent, also preferably carry out drying after mixing and ball milling, be more preferably spraying dry, obtain the second mixture; In this step, the method for ball milling is ball grinding method well known to those skilled in the art, there is no special restriction, and the rotating speed of this step ball milling is preferably 300 ~ 600rmp, is more preferably 400 ~ 600rmp, and the time of ball milling is preferably 2 ~ 6h, is more preferably 3 ~ 5h.
Step c) the second mixture will be obtained mix with the second carbon encapsulated material, ball milling, wherein said second carbon encapsulated material is carbon encapsulated material well known to those skilled in the art, there is no special restriction, in the present invention, be preferably one or more in glucose, sucrose, citric acid, phenolic resins, petroleum asphalt, benzene naphthalene dicarboxylic copolymer, epoxy resin, carboxymethyl cellulose, polyacrylonitrile, polyvinyl alcohol and polystyrene.The mass ratio of described second carbon encapsulated material and the second mixture is (5 ~ 20): (1 ~ 5), is preferably (5 ~ 10): (1 ~ 5).
Described step c) in the rotating speed of ball milling be preferably 300 ~ 600rmp, be more preferably 400 ~ 600rmp, the time of ball milling is preferably 2 ~ 6h, is more preferably 3 ~ 5h.
After second mixture and the second carbon encapsulated material mixing and ball milling, after preferably carrying out drying, then carry out roasting under the condition of inert gas shielding, obtain lithium ion battery negative material.The method of wherein said drying is method well known to those skilled in the art, there is no special restriction; Described inert gas is inert gas well known to those skilled in the art, there is no special restriction, is preferably argon gas in the present invention; The temperature of described roasting is preferably 500 DEG C ~ 900 DEG C, and be preferably 700 DEG C ~ 900 DEG C, the time of roasting is preferably 2 ~ 8h, is preferably 4 ~ 7h.After sintering, the first carbon encapsulated material forms carbon foam layer after foaming agent foam, and the second carbon encapsulated material forms amorphous carbon layer.
For increasing the toughness of carbon foam layer and amorphous carbon layer, described first carbon encapsulated material and the second carbon encapsulated material preferably also comprise one or more in Graphene, carbon nano-tube, carbon fiber, carbon black independently of one another; Its content is preferably 0.1% ~ 1% of the first mixture or the second mixture quality respectively.
Present invention also offers a kind of lithium ion battery, comprise positive pole, negative pole and electrolyte, wherein said positive pole and electrolyte are positive pole well known to those skilled in the art and electrolyte, there is no special restriction, and described negative pole comprises the lithium ion battery negative material prepared by said method.
In order to further illustrate the present invention, below in conjunction with embodiment, lithium ion battery cathode material and its preparation method provided by the invention, lithium ion battery are described in detail.
Reagent used in following examples is commercially available.
Embodiment 1
2g nano silica fume and 2g MCMB are placed in ball grinder by 1.1, take absolute ethyl alcohol as ball-milling medium, and 400rmp ball milling 8h, obtains the first mixture.
Add 4g glucose and 0.004g urea in 1.2 the first mixtures obtained in 1.1,450rpm ball milling 4h, obtains the second mixture after spray-dried.
Add 40g glucose in 1.3 the second mixtures obtained in 1.2,450rpm ball milling 4h, then by gained mixture in 80 DEG C of baking ovens after drying, in the tube furnace of argon atmosphere, 800 DEG C of roasting 5h, obtain lithium ion battery negative material.
The lithium ion battery negative material obtained in 1.3, SupperP and Kynoar binding agent are made into slurry with the ratio of 80:10:10, then be coated to equably in copper foil current collector, obtain cathode pole piece, using lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) as barrier film, 1mol/LLiPF 6(EC:DMC=1:1 volume ratio), as electrolyte, is assembled into battery in the glove box of argon shield.Battery is carried out constant current charge-discharge test on Land tester, and the multiplying power of discharge and recharge is 100mA/g, and charging/discharging voltage interval is 0.001 ~ 1.5V, obtains charging and discharging curve and sees Fig. 2, and wherein a is the lithium ion battery negative material obtained in 1.3; Obtain the rate charge-discharge curve of battery, as shown in Figure 3, wherein s is specific discharge capacity, and h is charge specific capacity; Obtain charge-discharge test and the results are shown in Table 1.
Embodiment 2
2g nano silica fume and 2g MCMB are placed in ball grinder by 2.1, take absolute ethyl alcohol as ball-milling medium, and 400rmp ball milling 8h, obtains the first mixture.
Add 0.8g glucose and 0.004g urea in 2.2 the first mixtures obtained in 2.1,450rpm ball milling 4h, obtains the second mixture after spray-dried.
Add 4.8g glucose in 2.3 the second mixtures obtained in 2.2,450rpm ball milling 4h, then by gained mixture in 80 DEG C of baking ovens after drying, in the tube furnace of argon atmosphere, 800 DEG C of roasting 5h, obtain lithium ion battery negative material.
The lithium ion battery negative material obtained in 2.3, SupperP and Kynoar binding agent are made into slurry with the ratio of 80:10:10, then be coated to equably in copper foil current collector, obtain cathode pole piece, using lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) as barrier film, 1mol/LLiPF 6(EC:DMC=1:1 volume ratio), as electrolyte, is assembled into battery in the glove box of argon shield.Battery is carried out constant current charge-discharge test on Land tester, and the multiplying power of discharge and recharge is 100mA/g, and charging/discharging voltage interval is 0.001 ~ 1.5V, obtains charging and discharging curve and sees Fig. 2, and wherein b is the lithium ion battery negative material obtained in 2.3; Obtain charge-discharge test and the results are shown in Table 1.
Embodiment 3
1g nano silica fume and 2g MCMB are placed in ball grinder by 3.1, take absolute ethyl alcohol as ball-milling medium, and 400rmp ball milling 8h, obtains the first mixture.
Add 30g glucose and 0.6g urea in 3.2 the first mixtures obtained in 3.1,450rpm ball milling 4h, obtains the second mixture after spray-dried.
Add 132g polyacrylonitrile in 3.3 the second mixtures obtained in 3.2,450rpm ball milling 4h, then by gained mixture in 80 DEG C of baking ovens after drying, in the tube furnace of argon atmosphere, 800 DEG C of roasting 5h, obtain lithium ion battery negative material.
The lithium ion battery negative material obtained in 3.3, SupperP and Kynoar binding agent are made into slurry with the ratio of 80:10:10, then be coated to equably in copper foil current collector, obtain cathode pole piece, using lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) as barrier film, 1mol/LLiPF 6(EC:DMC=1:1 volume ratio), as electrolyte, is assembled into battery in the glove box of argon shield.Battery is carried out constant current charge-discharge test on Land tester, and the multiplying power of discharge and recharge is 100mA/g, and charging/discharging voltage interval is 0.001 ~ 1.5V, obtains charge-discharge test and the results are shown in Table 1.
Embodiment 4
2g nano silica fume and 1g carbon nano-tube are placed in ball grinder by 4.1, take anhydrous propanone as ball-milling medium, and 400rmp ball milling 8h, obtains the first mixture.
Add 6g phenolic resins and 0.6g unifor in 4.2 the first mixtures obtained in 4.1,450rpm ball milling 4h, obtains the second mixture after spray-dried.
Add 9g phenolic resins in 4.3 the second mixtures obtained in 4.2,450rpm ball milling 4h, then by gained mixture in 80 DEG C of baking ovens after drying, in the tube furnace of argon atmosphere, 800 DEG C of roasting 5h, obtain lithium ion battery negative material.
The lithium ion battery negative material obtained in 4.3, SupperP and Kynoar binding agent are made into slurry with the ratio of 80:10:10, then be coated to equably in copper foil current collector, obtain cathode pole piece, using lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) as barrier film, 1mol/LLiPF 6(EC:DMC=1:1 volume ratio), as electrolyte, is assembled into battery in the glove box of argon shield.Battery is carried out constant current charge-discharge test on Land tester, and the multiplying power of discharge and recharge is 100mA/g, and charging/discharging voltage interval is 0.001 ~ 1.5V, obtains charge-discharge test and the results are shown in Table 1.
Embodiment 5
2g nano silica fume and 3g celion are placed in ball grinder by 5.1, and with anhydrous carbon tetrachloride for ball-milling medium, 400rmp ball milling 8h, obtains the first mixture.
Add 2.5g pitch in 5.2 the first mixtures obtained in 5.1,0.05g Graphene and 0.5g urea, 450rpm ball milling 4h, obtains the second mixture after spray-dried.
Add 7.5g pitch in 5.3 the second mixtures obtained in 5.2,450rpm ball milling 4h, then by gained mixture in 80 DEG C of baking ovens after drying, in the tube furnace of argon atmosphere, 800 DEG C of roasting 5h, obtain lithium ion battery negative material.
The lithium ion battery negative material obtained in 5.3, SupperP and Kynoar binding agent are made into slurry with the ratio of 80:10:10, then be coated to equably in copper foil current collector, obtain cathode pole piece, using lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) as barrier film, 1mol/LLiPF 6(EC:DMC=1:1 volume ratio), as electrolyte, is assembled into battery in the glove box of argon shield.Battery is carried out constant current charge-discharge test on Land tester, and the multiplying power of discharge and recharge is 100mA/g, and charging/discharging voltage interval is 0.001 ~ 1.5V, obtains charge-discharge test and the results are shown in Table 1.
Embodiment 6
1g nano silica fume and 3g celion are placed in ball grinder by 6.1, and with anhydrous carbon tetrachloride for ball-milling medium, 400rmp ball milling 8h, obtains the first mixture.
Add 8g pitch and 0.8g urea in 6.2 the first mixtures obtained in 6.1,450rpm ball milling 4h, obtains the second mixture after spray-dried.
7.5g pitch and 0.06g carbon nano-tube is added in 6.3 the second mixtures obtained in 6.2,450rpm ball milling 4h, then by gained mixture in 80 DEG C of baking ovens after drying, in the tube furnace of argon atmosphere, 800 DEG C of roasting 5h, obtain lithium ion battery negative material.
The lithium ion battery negative material obtained in 6.3, SupperP and Kynoar binding agent are made into slurry with the ratio of 80:10:10, then be coated to equably in copper foil current collector, obtain cathode pole piece, using lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) as barrier film, 1mol/LLiPF 6(EC:DMC=1:1 volume ratio), as electrolyte, is assembled into battery in the glove box of argon shield.Battery is carried out constant current charge-discharge test on Land tester, and the multiplying power of discharge and recharge is 100mA/g, and charging/discharging voltage interval is 0.001 ~ 1.5V, obtains charge-discharge test and the results are shown in Table 1.
Table 1 lithium ion battery negative material charge-discharge test result
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (8)

1. a preparation method for lithium ion battery negative material, is characterized in that, comprises the following steps:
A) by silica flour and material with carbon element mixing and ball milling, the first mixture is obtained;
B) described first mixture, the first carbon encapsulated material are mixed with blowing agent, ball milling, obtain the second mixture;
C) mixed with the second carbon encapsulated material by described second mixture, ball milling, then roasting under inert gas shielding, obtains lithium ion battery negative material.
2. preparation method according to claim 1, it is characterized in that, described first carbon encapsulated material and the second carbon encapsulated material are selected from one or more in glucose, sucrose, citric acid, phenolic resins, petroleum asphalt, benzene naphthalene dicarboxylic copolymer, epoxy resin, carboxymethyl cellulose, polyacrylonitrile, polyvinyl alcohol and polystyrene independently of one another.
3. preparation method according to claim 2, is characterized in that, described first carbon encapsulated material and the second carbon encapsulated material also comprise one or more in Graphene, carbon nano-tube, carbon fiber and carbon black independently of one another.
4. preparation method according to claim 1, is characterized in that, described blowing agent is selected from one or more in azodiisobutyronitrile, Celogen Az, benzene sulfonyl hydrazide, unifor, benzene diazonium aminobenzene and urea.
5. preparation method according to claim 1, is characterized in that, the quality of described blowing agent is 0.1% ~ 20% of the first mixture quality.
6. preparation method according to claim 1, is characterized in that, the mass ratio of described first carbon encapsulated material and the first mixture is (1 ~ 10): (1 ~ 5).
7. preparation method according to claim 1, is characterized in that, the mass ratio of described second carbon encapsulated material and the second mixture is (5 ~ 20): (1 ~ 5).
8. a lithium ion battery, is characterized in that, comprises the lithium ion battery negative material prepared by claim 1 ~ 7 any one preparation method.
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