CN103346293A - Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery - Google Patents
Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery Download PDFInfo
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Abstract
The invention provides a lithium ion battery cathode material and a preparation method of the lithium ion battery cathode material as well as a lithium ion battery. The lithium ion battery cathode material comprises an inner core, a middle layer outside the inner core and an outer shell wrapping the middle layer, the inner core is Si-C particles, the middle layer is a foam layer, the outer shell is an amorphous carbon layer and the Si-C particles are formed by Si particles and C materials. Compared with the prior art, a middle carbon foam layer existing between the Si-C particle inner core and the amorphous carbon outer shell can form an conductive network structure, thus improving conductivity of a material and buffering enormous volume change of Si particles in the charge-discharge processes; and the amorphous carbon outer shell layer can maintain the core-shell structure of the cathode material, and the cladding layer of the core-shell structure can buffer the volume change, improve cycling stability of electrodes, reduce contact between active substances and an electrolyte, improve first coulombic efficiency of an electrode, prevent nanoparticle aggregation and enhance electrode conductivity.
Description
Technical field
The invention belongs to technical field of electrochemistry, relate in particular to lithium ion battery cathode material and its preparation method, lithium ion battery.
Background technology
Lithium ion battery has operating voltage height, specific energy height, operating temperature range is wide, discharge is steady, volume is little, quality is light, memory-less effect and advantage such as environmentally friendly, has therefore showed wide application prospect in fields such as portable electric appts, electric automobile, space technology, national defense industry.And, along with mobile electronic equipment growing to high power capacity, long-life batteries demand, people are to the demands for higher performance of lithium ion battery, and negative material has worldwide obtained research widely as the key factor that improves lithium ion battery energy and cycle life.
At the beginning of the end of the year 90 of 20th century, Sony corporation of Japan takes the lead in developing carbon negative pole material, has significantly improved security performance and the charge and discharge circulation life of lithium ion battery.Yet, the theoretical specific capacity of carbon negative pole material has only 372mAh/g, its energy density can't satisfy present various electronic equipment for consumption, especially energy storage device and electric motor car to the requirement of energy density, therefore presses for to seek a kind of negative material that can replace the high-energy-density of material with carbon element.
Wherein, the 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 reserves in the earth's crust are abundant.Yet in charge and discharge process, the reaction of the removal lithium embedded of silicon will be followed 310% change in volume, very easily cause the cracking of electrode and coming off of active material, thereby cause the deterioration of electrode cycle performance.
Serious bulk effect at silicon materials, need it is carried out modification to improve cycle performance, one of them effective method prepares Si-C composite material exactly, make it have nucleocapsid structure, namely coat one deck carbon simple substance on the surface of silicon grain, can suppress the efflorescence of silicon grain like this and can avoid contingent silicon grain agglomeration in the charge and discharge process again.
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, the acquisition composite negative pole material shatters, sieves.This composite negative pole material is a kind of nucleocapsid structure, and the content range of elemental silicon is 0.01～10% in the material, and the carbon content scope is 90～99.9%.The Si-C composite material that this kind method obtains has some improvement to the shortcoming of existing silicon-carbon cathode material cycle performance difference, but the structure denser of outer field amorphous carbon layer, in charge and discharge process, because the enormousness of silicon changes, easy to crack, efflorescence cause electrode cycle performance variation, and 0.5C discharges and recharges, the conservation rate of 50 circulation back capacity only is 63%, high rate performance is relatively poor, remains further to be improved.
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, the intermediate layer that comprise kernel, is wrapped in described kernel outside and the shell that is wrapped in outside, described intermediate layer, described kernel is the silicon-carbon particle, and described intermediate layer is carbon foam layer, and described shell is amorphous carbon layer; Described silicon-carbon particle 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 μ m.
Preferably, the particle diameter of described lithium ion battery negative material is 10～50 μ m.
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 the carbon nano-tube.
The present invention also provides a kind of preparation method of lithium ion battery negative material, may further comprise the steps:
A) with silica flour and material with carbon element mixing and ball milling, obtain first mixture;
B) described first mixture, first carbon encapsulated material are mixed with blowing agent, ball milling obtains second mixture;
C) described second mixture is mixed with second carbon encapsulated material, ball milling, roasting under inert gas shielding obtains lithium ion battery negative material then.
Preferably, described first carbon encapsulated material and 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 the polystyrene independently of one another.
Preferably, described first carbon encapsulated material and second carbon encapsulated material also comprise one or more in Graphene, carbon nano-tube, carbon fiber, the 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 the urea.
Preferably, the quality of described blowing agent is 0.1%～20% of first mixture quality.
Preferably, the mass ratio of described first carbon encapsulated material and first mixture is (1～10): (1～5).
Preferably, the mass ratio of described second carbon encapsulated material and second mixture is (5～20): (1～5).
The present invention also provides a kind of lithium ion battery, comprises 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 and the shell that is wrapped in outside the described intermediate layer of described kernel outside, described kernel is the silicon-carbon particle, the intermediate layer is carbon foam layer, and shell is amorphous carbon layer; Described silicon-carbon particle is formed by silicon grain and material with carbon element.Compare with the silicon-carbon composite cathode material of prior art nucleocapsid structure, the present invention comprises the intermediate layer carbon foam layer between silicon-carbon particle kernel and amorphous carbon shell, at first carbon foam layer can constitute the conductive grid structure, this structure can not only improve the electric conductivity of material, and the enormousness of silicon grain changes in the available buffer charge and discharge process; Secondly, the outer shell amorphous carbon layer can further be kept the nucleocapsid structure of negative material, the coating layer available buffer change in volume of nucleocapsid structure, reduce stress, improve the cyclical stability of electrode, the minimizing active material contacts with electrolyte, improve the efficient of enclosed pasture first of electrode, also can stop nanoparticle agglomerates, improve electrode conductivuty, so the present invention further is improved the cyclical stability of lithium ion battery negative material and high rate performance by carbon foam layer and amorphous carbon layer combination.
Description of drawings
Fig. 1 is the structural representation of lithium ion battery negative material of the present invention;
Fig. 2 prepares battery for the lithium ion battery negative material that is obtained by the embodiment of the invention 1 and is prepared the charging and discharging curve of battery by the lithium ion battery negative material that embodiment 2 obtains;
Fig. 3 prepares the rate charge-discharge curve of battery for the lithium ion battery negative material that is obtained by the embodiment of the invention 1.
Embodiment
The invention provides a kind of lithium ion battery negative material, the intermediate layer that comprise kernel, is wrapped in described kernel outside and the shell that is wrapped in outside, described intermediate layer, described kernel is the silicon-carbon particle, and the intermediate layer is carbon foam layer, and shell is amorphous carbon layer; Described silicon-carbon particle is formed by silicon grain and material with carbon element.Its schematic diagram as shown in Figure 1, wherein 1 is the shell amorphous carbon layer, 2 and 3 is the silicon-carbon particle, 2 is material with carbon element, 3 is silicon grain, 4 is the intermediate layer carbon foam layer.
Wherein, the particle diameter of lithium ion battery negative material of the present invention is 10～50 μ m, is preferably 15～40 μ m; The content of silicon is preferably 10～50wt% in this negative material, 20～40wt% more preferably, and carbon content is preferably 50～90wt%, more preferably 60～80wt%.
The silicon-carbon particle 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 less relatively, has stable circulation performance preferably, and good conductivity, and the chemical property of silicon and carbon is close, the two can be combined closely, therefore with the basis material (be dispersible carrier) of material with carbon element as the dispersed silicon particle, with the inner nuclear material of silicon-carbon particle as negative material.Described material with carbon element is that material with carbon element well known to those skilled in the art gets final product, there is no special restriction, be preferably in native graphite, Delanium, celion, petroleum coke, needle coke, carbon fiber, MCMB and the carbon nano-tube one or more among the present invention.
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 constitute the conductive grid structure on the one hand, improves the electric conductivity of negative material, and on the other hand, this structure can give the space of change in volume, and the enormousness that cushions silicon grain in the charge and discharge process effectively changes.
Amorphous carbon layer constitutes the shell of lithium ion battery negative material of the present invention, and its thickness is 1～10 μ m, is preferably 3～8 μ m.Amorphous carbon layer is the amorphous carbon layer that constitutes the nucleocapsid structure shell in the lithium ion battery negative material well known to those skilled in the art, there is no special restriction.Amorphous carbon layer can further be kept the nucleocapsid structure of negative material, the coating layer available buffer change in volume of nucleocapsid structure, reduce stress, improve the cyclical stability of electrode, the minimizing active material contacts with electrolyte, improve the efficient of enclosed pasture 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 are further improved the cyclical stability of lithium ion battery negative material and high rate performance.
The present invention also provides the preparation method of above-mentioned lithium ion battery negative material, may further comprise the steps: a) with silica flour and material with carbon element mixing and ball milling, obtain first mixture; B) described first mixture, first carbon encapsulated material are mixed with blowing agent, ball milling obtains second mixture; C) described second mixture is mixed with second carbon encapsulated material, ball milling, roasting under inert gas shielding obtains lithium ion battery negative material then.
Wherein, with silica flour and material with carbon element mixing and ball milling, obtain first mixture, this mixture is the kernel silicon-carbon particle of lithium ion battery negative material.Described silica flour is that silica flour well known to those skilled in the art gets final product, and there is no special restriction, can be nano-dispersed between material with carbon element for making silicon grain, 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); The method of ball milling there is no special restriction for those skilled in the art's well-known process gets final product in the described step a), and is even for ball milling, preferably adopts 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, more preferably 300～500rmp; The time of described ball milling is preferably 5～10h, more preferably 6～8h.
Add first carbon encapsulated material and blowing agent in first mixture, mixing and ball milling obtains second mixture.Wherein, behind the preferred ball milling through spray drying.Wherein, described first carbon encapsulated material is that the material with carbon element that can be used for coating well known to those skilled in the art gets final product, there is no special restriction, be preferably in glucose, sucrose, citric acid, phenolic resins, petroleum asphalt, benzene naphthalene dicarboxylic copolymer, epoxy resin, carboxymethyl cellulose, polyacrylonitrile, polyvinyl alcohol and the polystyrene one or more among the present invention; The mass ratio of described first carbon encapsulated material and first mixture is preferably (1～10): (1～5), more preferably (1～6): (1～2); Described blowing agent is that blowing agent well known to those skilled in the art gets final product, and there is no special restriction, is preferably in azodiisobutyronitrile, Celogen Az, benzene sulfonyl hydrazide, unifor, benzene diazonium aminobenzene and the urea one or more; The quality of described blowing agent is 0.1%～20% of first mixture quality, is preferably 1%～15%.
Among the present invention, add first carbon encapsulated material and blowing agent in first mixture, also preferably carry out drying after the mixing and ball milling, more preferably spray drying obtains second mixture; The method of ball milling is that ball grinding method well known to those skilled in the art gets final product in this step, there is no special restriction, and the rotating speed of this step ball milling is preferably 300～600rmp, 400～600rmp more preferably, and the time of ball milling is preferably 2～6h, more preferably 3～5h.
Step c) will obtain second mixture and mix with second carbon encapsulated material, ball milling, wherein said second carbon encapsulated material is that carbon encapsulated material well known to those skilled in the art gets final product, there is no special restriction, be preferably in glucose, sucrose, citric acid, phenolic resins, petroleum asphalt, benzene naphthalene dicarboxylic copolymer, epoxy resin, carboxymethyl cellulose, polyacrylonitrile, polyvinyl alcohol and the polystyrene one or more among the present invention.The mass ratio of described second carbon encapsulated material and second mixture is (5～20): (1～5) is preferably (5～10): (1～5).
The rotating speed of ball milling is preferably 300～600rmp in the described step c), 400～600rmp more preferably, and the time of ball milling is preferably 2～6h, more preferably 3～5h.
After second mixture and the second carbon encapsulated material mixing and ball milling, preferably carry out drying after, under the condition of inert gas shielding, carry out roasting again, obtain lithium ion battery negative material.The method of wherein said drying is that method well known to those skilled in the art gets final product, and there is no special restriction; Described inert gas is that inert gas well known to those skilled in the art gets final product, and there is no special restriction, is preferably argon gas among the present invention; The temperature of described roasting is preferably 500 ℃～900 ℃, is preferably 700 ℃～900 ℃, and the time of roasting is preferably 2～8h, is preferably 4～7h.First carbon encapsulated material forms carbon foam layer behind the sintering after the blowing agent foaming, and 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 second carbon encapsulated material preferably also comprise one or more in Graphene, carbon nano-tube, carbon fiber, the carbon black independently of one another; Its content is preferably 0.1%～1% of first mixture or second mixture quality respectively.
The present invention also provides a kind of lithium ion battery, comprise positive pole, negative pole and electrolyte, wherein said positive pole and electrolyte are that positive pole well known to those skilled in the art and electrolyte get final product, and there is no special restriction, and described negative pole comprises the prepared lithium ion battery negative material of said method.
In order to further specify 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.
Used reagent is commercially available in following examples.
1.1 2g nano silica fume and 2g MCMB are placed ball grinder, be ball-milling medium with the absolute ethyl alcohol, 400rmp ball milling 8h obtains first mixture.
1.2 add 4g glucose and 0.004g urea in first mixture that obtains in 1.1,450rpm ball milling 4h obtains second mixture after spray-dried.
1.3 add 40g glucose in second mixture that in 1.2, obtains, 450rpm ball milling 4h, then with the gained mixture in 80 ℃ of baking ovens after the drying, 800 ℃ of roasting 5h obtain lithium ion battery negative material in the tube furnace of argon atmosphere.
The lithium ion battery negative material, Supper P and the Kynoar binding agent that obtain in 1.3 are made into slurry with the ratio of 80:10:10, be coated on the Copper Foil collector then equably, obtain cathode pole piece, with lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) is as barrier film, 1mol/L LiPF
6(EC:DMC=1:1 volume ratio) is assembled into battery as electrolyte in the glove box of argon shield.Battery is carried out the constant current charge-discharge test at the Land tester, and the multiplying power that discharges and recharges is 100mA/g, and the 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 that obtains 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 the charge ratio capacity; Obtain charge-discharge test and the results are shown in Table 1.
2.1 2g nano silica fume and 2g MCMB are placed ball grinder, be ball-milling medium with the absolute ethyl alcohol, 400rmp ball milling 8h obtains first mixture.
2.2 add 0.8g glucose and 0.004g urea in first mixture that obtains in 2.1,450rpm ball milling 4h obtains second mixture after spray-dried.
2.3 add 4.8g glucose in second mixture that in 2.2, obtains, 450rpm ball milling 4h, then with the gained mixture in 80 ℃ of baking ovens after the drying, 800 ℃ of roasting 5h obtain lithium ion battery negative material in the tube furnace of argon atmosphere.
The lithium ion battery negative material, Supper P and the Kynoar binding agent that obtain in 2.3 are made into slurry with the ratio of 80:10:10, be coated on the Copper Foil collector then equably, obtain cathode pole piece, with lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) is as barrier film, 1mol/L LiPF
6(EC:DMC=1:1 volume ratio) is assembled into battery as electrolyte in the glove box of argon shield.Battery is carried out the constant current charge-discharge test at the Land tester, and the multiplying power that discharges and recharges is 100mA/g, and the 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 that obtains in 2.3; Obtain charge-discharge test and the results are shown in Table 1.
3.1 1g nano silica fume and 2g MCMB are placed ball grinder, be ball-milling medium with the absolute ethyl alcohol, 400rmp ball milling 8h obtains first mixture.
3.2 add 30g glucose and 0.6g urea in first mixture that obtains in 3.1,450rpm ball milling 4h obtains second mixture after spray-dried.
3.3 add the 132g polyacrylonitrile in second mixture that in 3.2, obtains, 450rpm ball milling 4h, then with the gained mixture in 80 ℃ of baking ovens after the drying, 800 ℃ of roasting 5h obtain lithium ion battery negative material in the tube furnace of argon atmosphere.
The lithium ion battery negative material, Supper P and the Kynoar binding agent that obtain in 3.3 are made into slurry with the ratio of 80:10:10, be coated on the Copper Foil collector then equably, obtain cathode pole piece, with lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) is as barrier film, 1mol/L LiPF
6(EC:DMC=1:1 volume ratio) is assembled into battery as electrolyte in the glove box of argon shield.Battery is carried out the constant current charge-discharge test at the Land tester, and the multiplying power that discharges and recharges is 100mA/g, and the charging/discharging voltage interval is 0.001～1.5V, obtains charge-discharge test and the results are shown in Table 1.
4.1 2g nano silica fume and 1g carbon nano-tube are placed ball grinder, be ball-milling medium with the anhydrous propanone, 400rmp ball milling 8h obtains first mixture.
4.2 add 6g phenolic resins and 0.6g unifor in first mixture that obtains in 4.1,450rpm ball milling 4h obtains second mixture after spray-dried.
4.3 add 9g phenolic resins in second mixture that in 4.2, obtains, 450rpm ball milling 4h, then with the gained mixture in 80 ℃ of baking ovens after the drying, 800 ℃ of roasting 5h obtain lithium ion battery negative material in the tube furnace of argon atmosphere.
The lithium ion battery negative material, Supper P and the Kynoar binding agent that obtain in 4.3 are made into slurry with the ratio of 80:10:10, be coated on the Copper Foil collector then equably, obtain cathode pole piece, with lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) is as barrier film, 1mol/L LiPF
6(EC:DMC=1:1 volume ratio) is assembled into battery as electrolyte in the glove box of argon shield.Battery is carried out the constant current charge-discharge test at the Land tester, and the multiplying power that discharges and recharges is 100mA/g, and the charging/discharging voltage interval is 0.001～1.5V, obtains charge-discharge test and the results are shown in Table 1.
Embodiment 5
5.1 2g nano silica fume and 3g celion are placed ball grinder, be ball-milling medium with anhydrous carbon tetrachloride, 400rmp ball milling 8h obtains first mixture.
5.2 add 2.5g pitch in first mixture that in 5.1, obtains, 0.05g Graphene and 0.5g urea, 450rpm ball milling 4h obtains second mixture after spray-dried.
5.3 add 7.5g pitch in second mixture that in 5.2, obtains, 450rpm ball milling 4h, then with the gained mixture in 80 ℃ of baking ovens after the drying, 800 ℃ of roasting 5h obtain lithium ion battery negative material in the tube furnace of argon atmosphere.
The lithium ion battery negative material, Supper P and the Kynoar binding agent that obtain in 5.3 are made into slurry with the ratio of 80:10:10, be coated on the Copper Foil collector then equably, obtain cathode pole piece, with lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) is as barrier film, 1mol/L LiPF
6(EC:DMC=1:1 volume ratio) is assembled into battery as electrolyte in the glove box of argon shield.Battery is carried out the constant current charge-discharge test at the Land tester, and the multiplying power that discharges and recharges is 100mA/g, and the charging/discharging voltage interval is 0.001～1.5V, obtains charge-discharge test and the results are shown in Table 1.
Embodiment 6
6.1 1g nano silica fume and 3g celion are placed ball grinder, be ball-milling medium with anhydrous carbon tetrachloride, 400rmp ball milling 8h obtains first mixture.
6.2 add 8g pitch and 0.8g urea in first mixture that obtains in 6.1,450rpm ball milling 4h obtains second mixture after spray-dried.
6.3 add 7.5g pitch and 0.06g carbon nano-tube in second mixture that in 6.2, obtains, 450rpm ball milling 4h, then with the gained mixture in 80 ℃ of baking ovens after the drying, 800 ℃ of roasting 5h obtain lithium ion battery negative material in the tube furnace of argon atmosphere.
The lithium ion battery negative material, Supper P and the Kynoar binding agent that obtain in 6.3 are made into slurry with the ratio of 80:10:10, be coated on the Copper Foil collector then equably, obtain cathode pole piece, with lithium metal as to electrode, microporous polypropylene membrane (Celgard2400) is as barrier film, 1mol/L LiPF
6(EC:DMC=1:1 volume ratio) is assembled into battery as electrolyte in the glove box of argon shield.Battery is carried out the constant current charge-discharge test at the Land tester, and the multiplying power that discharges and recharges is 100mA/g, and the 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 only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 (13)
1. lithium ion battery negative material, it is characterized in that, the intermediate layer that comprise kernel, is wrapped in described kernel outside and the shell that is wrapped in outside, described intermediate layer, described kernel is the silicon-carbon particle, described intermediate layer is carbon foam layer, and described shell is amorphous carbon layer; Described silicon-carbon particle is formed by silicon grain and material with carbon element.
2. lithium ion battery negative material according to claim 1 is characterized in that, the thickness in described intermediate layer is 50～100nm.
3. lithium ion battery negative material according to claim 1 is characterized in that, the thickness of described shell is 1～10 μ m.
4. lithium ion battery negative material according to claim 1 is characterized in that, the particle diameter of described lithium ion battery negative material is 10～50 μ m.
5. preparation method according to claim 1 is characterized in that, described material with carbon element is selected from one or more in native graphite, Delanium, celion, petroleum coke, needle coke, carbon fiber, MCMB and the carbon nano-tube.
6. the preparation method of a lithium ion battery negative material is characterized in that, may further comprise the steps:
A) with silica flour and material with carbon element mixing and ball milling, obtain first mixture;
B) described first mixture, first carbon encapsulated material are mixed with blowing agent, ball milling obtains second mixture;
C) described second mixture is mixed with second carbon encapsulated material, ball milling, roasting under inert gas shielding obtains lithium ion battery negative material then.
7. preparation method according to claim 6, it is characterized in that described first carbon encapsulated material and 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 the polystyrene independently of one another.
8. preparation method according to claim 7 is characterized in that, described first carbon encapsulated material and second carbon encapsulated material also comprise one or more in Graphene, carbon nano-tube, carbon fiber and the carbon black independently of one another.
9. preparation method according to claim 6 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 the urea.
10. preparation method according to claim 6 is characterized in that, the quality of described blowing agent is 0.1%～20% of first mixture quality.
11. preparation method according to claim 6 is characterized in that, the mass ratio of described first carbon encapsulated material and first mixture is (1～10): (1～5).
12. preparation method according to claim 6 is characterized in that, the mass ratio of described second carbon encapsulated material and second mixture is (5～20): (1～5).
13. a lithium ion battery is characterized in that, comprises any described lithium ion battery negative material of claim 1～5 or any prepared lithium ion battery negative material of claim 6～12.
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| CN104409709A (en) * | 2014-11-27 | 2015-03-11 | 中航锂电（洛阳）有限公司 | Lithium-ion battery negative electrode material, preparation method and lithium ion battery |
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| CN114284481A (en) * | 2021-12-23 | 2022-04-05 | 北京卫蓝新能源科技有限公司 | High-rate silicon-oxygen-carbon material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1937288A (en) * | 2005-09-23 | 2007-03-28 | 三星Sdi株式会社 | Anode active material, method of manufacturing the same, and lithium battery using the same |
| CN102255077A (en) * | 2010-05-21 | 2011-11-23 | 深圳市比克电池有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN202585627U (en) * | 2012-04-24 | 2012-12-05 | 东华大学 | Structure of cathode material of lithium ion battery |
| CN102931409A (en) * | 2012-10-25 | 2013-02-13 | 中国计量学院 | Preparation method of polyaniline/silicon composite with core-shell structure for lithium ion battery cathode |
| CN103000863A (en) * | 2012-10-16 | 2013-03-27 | 华南师范大学 | Sn-Co/C alloy cathode material of lithium ion battery and preparation method thereof |
| CN103094533A (en) * | 2012-11-26 | 2013-05-08 | 中南大学 | Multi-core core-shell-structure silicon carbon composite negative pole material and preparation method thereof |
-
2013
- 2013-06-28 CN CN201310272311.9A patent/CN103346293B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1937288A (en) * | 2005-09-23 | 2007-03-28 | 三星Sdi株式会社 | Anode active material, method of manufacturing the same, and lithium battery using the same |
| CN102255077A (en) * | 2010-05-21 | 2011-11-23 | 深圳市比克电池有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN202585627U (en) * | 2012-04-24 | 2012-12-05 | 东华大学 | Structure of cathode material of lithium ion battery |
| CN103000863A (en) * | 2012-10-16 | 2013-03-27 | 华南师范大学 | Sn-Co/C alloy cathode material of lithium ion battery and preparation method thereof |
| CN102931409A (en) * | 2012-10-25 | 2013-02-13 | 中国计量学院 | Preparation method of polyaniline/silicon composite with core-shell structure for lithium ion battery cathode |
| CN103094533A (en) * | 2012-11-26 | 2013-05-08 | 中南大学 | Multi-core core-shell-structure silicon carbon composite negative pole material and preparation method thereof |
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