CN108493437A - A method of preparing tin carbon lithium ion negative material - Google Patents
A method of preparing tin carbon lithium ion negative material Download PDFInfo
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- CN108493437A CN108493437A CN201810223973.XA CN201810223973A CN108493437A CN 108493437 A CN108493437 A CN 108493437A CN 201810223973 A CN201810223973 A CN 201810223973A CN 108493437 A CN108493437 A CN 108493437A
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Abstract
The present invention discloses a kind of method preparing tin carbon lithium ion negative material, includes following steps：（1）The doping vario-property of stannic oxide：Weigh constant weight nano-stannic oxide and cuprous oxide by 100：10 50 ratio carries out dry ball milling mixing 1h；Then it places in atmosphere furnace and carries out carbon thermal reduction；（2）The compound of stannic oxide modified product and graphite；（3）Secondary coating modification；The present invention is doped modification using cuprous oxide to stannic oxide, reduces the expansion characteristics of tin carbon complex, improves cycle performance；Using compression molding, shaping process progress secondary granulation is roasted and breaks up, the time is short, simple for process, easily realizes industrialization large-scale production；It realizes stannic oxide and graphite simultaneously, the advantages of granulation between graphite and graphite, and can realize the function of carrying out surface modification to stannic oxide and graphite；It can be obviously improved the surface defect generated during secondary granulation using secondary cladding, promote the first charge discharge efficiency and cycle performance of product.
Description
Technical field
The present invention relates to negative material field technologies, refer in particular to a kind of method preparing tin carbon lithium ion negative material.
Background technology
With the development of science and technology, social progress, people to high-energy-density, high power, the long-life, safety and environmental protection it is secondary
The demand of battery is increasingly enhanced.Traditional carbon negative pole material cannot meet lithium ion battery high-energy of new generation, high power
Requirement, therefore develop novel high-capacity non-carbon negative material have very important significance.
The actual capacity of graphite type material has been approached theoretical capacity at present（372mAh/g）, the space further promoted is non-
It is often limited；Metal Sn and its oxide can form alloy with Li, and theoretical capacity is 994 mAh/g, is twice of graphite type material
It is more, while tin-based material is also equipped with security performance height, good rate capability, compatible with electrolyte as lithium ion battery negative material
Property good, inexpensive environmental protection the features such as, be most potential one of next-generation lithium ion battery negative material.And tin-based material is deposited at present
Greatest problem be exactly that cycle performance is not good enough, this is mainly due to Sn during with Li alloyings/removal alloying, volume
It can occur greatly to change, so as to cause the gradual strain cracking of electrode material, and then dusting, failure.
Invention content
In view of this, preparing tin carbon lithium in view of the deficiencies of the prior art, the present invention aims to provide a kind of
The method of ion negative material can improve production efficiency, reduce manufacturing cost, quickly and effectively prepares product and improve tinbase
Negative material volume expansion improves the cycle performance and capacity retention ratio of battery.
To achieve the above object, the present invention is using following technical solution：
A method of tin carbon lithium ion negative material is prepared, includes following steps：
（1）The doping vario-property of stannic oxide：Weigh constant weight nano-stannic oxide and cuprous oxide by 100：The ratio of 10-50
Example carries out dry ball milling mixing 1h；Then it places in atmosphere furnace and carries out carbon thermal reduction, be warming up under nitrogen protection with 5 DEG C/min
700-950 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains stannic oxide modified product；
（2）The compound of stannic oxide modified product and graphite：Stannic oxide modified product is subjected to 400 mesh sievings, takes it
Minus mesh is with graphite, pitch, phenolic resin in proportion with V-arrangement mixing machine 25Hz mixing 1h, and its ratio be graphite：Stannic oxide changes
Property product：Pitch：Phenolic resin=100：15：5-20：3-15；Mixture is put into moulding press, briquetting is carried out with 15-20MPa
Molding, then puts molding materials into firing chamber and roasts, in a nitrogen atmosphere with the speed of 5 DEG C/min since room temperature
Degree is warming up to 150 DEG C, 90 min of constant temperature, then is warming up to 600 DEG C with the speed of 5 DEG C/min, 240 min of constant temperature；It is cooling
To room temperature, it is broken just broken that Hubei Province carried out to molding materials, carries out breaing up shaping subsequently into roll mill, d50 is controlled at 12-14 μm,
Tentatively obtain the compound secondary granulation product of tin carbon；
（3）Secondary coating modification：By step（2）The compound secondary granulation product of tin carbon obtained presses 100 with hard pitch：3-10's
Then ratio V-arrangement mixing machine 25Hz mixing 1h are placed in atmosphere furnace and are carried out carbon thermal reduction, under nitrogen protection with 5 DEG C/min
It is warming up to 800-1050 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains final secondary coating modification product.
As a preferred embodiment, described to state step（2）Graphite is high-purity natural spherical graphite, and d50 is 8-10 μm.
As a preferred embodiment, the step（2）Middle pitch is mid temperature pitch, and d50 is 4-6 μm.
As a preferred embodiment, the step（2）The d50 of middle phenolic resin is 4-6 μm.
The present invention has clear advantage and advantageous effect compared with prior art, specifically, by above-mentioned technical proposal
Known to：
The present invention is doped modification using cuprous oxide to stannic oxide, reduces the expansion characteristics of tin carbon complex, is promoted
Cycle performance；Using compression molding, shaping process progress secondary granulation is roasted and breaks up, the time is short, simple for process, easily realizes
Industrialization large-scale production；It realizes stannic oxide and graphite simultaneously, the advantages of granulation between graphite and graphite, and can realize to two
Tin oxide and graphite carry out the function of surface modification；The table generated during secondary granulation can be obviously improved using secondary cladding
Planar defect promotes the first charge discharge efficiency and cycle performance of product.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the tin-carbon composite product that the present invention obtains；
Fig. 2 is the simulated battery test curve figure for the tin-carbon composite product that the present invention obtains.
Specific implementation mode
Present invention is disclosed a kind of methods preparing tin carbon lithium ion negative material, include following steps：
（1）The doping vario-property of stannic oxide：Weigh constant weight nano-stannic oxide and cuprous oxide by 100：The ratio of 10-50
Example carries out dry ball milling mixing 1h；Then it places in atmosphere furnace and carries out carbon thermal reduction, be warming up under nitrogen protection with 5 DEG C/min
700-950 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains stannic oxide modified product.
（2）The compound of stannic oxide modified product and graphite：Stannic oxide modified product is subjected to 400 mesh sievings,
Take its minus mesh with graphite, pitch, phenolic resin in proportion with V-arrangement mixing machine 25Hz mixing 1h, its ratio be graphite：Titanium dioxide
Tin modification product：Pitch：Phenolic resin=100：15：5-20：3-15；Mixture is put into moulding press and is carried out with 15-20MPa
Then compound stalk forming is put molding materials into firing chamber and is roasted, in a nitrogen atmosphere with 5 DEG C/min since room temperature
Speed be warming up to 150 DEG C, 90 min of constant temperature, then be warming up to 600 DEG C with the speed of 5 DEG C/min, 240 min of constant temperature；
It is cooled to room temperature, it is broken just broken to carry out Hubei Province to molding materials, carries out breaing up shaping subsequently into roll mill, d50 is controlled in 12-14
μm, tentatively obtain the compound secondary granulation product of tin carbon.The graphite is high-purity natural spherical graphite, and d50 is 8-10 μm, described
Pitch is mid temperature pitch, and d50 is 4-6 μm, and the d50 of the phenolic resin is 4-6 μm.
（3）Secondary coating modification：By step（2）The compound secondary granulation product of tin carbon obtained presses 100 with hard pitch：3-
10 ratio V-arrangement mixing machine 25Hz mixing 1h, then place atmosphere furnace in carry out carbon thermal reduction, under nitrogen protection with 5 DEG C/
Min is warming up to 800-1050 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains final secondary coating modification product.
With multiple embodiments, invention is further described in detail below：
Embodiment 1：
A method of tin carbon lithium ion negative material is prepared, includes following steps：
（1）The doping vario-property of stannic oxide：Weigh constant weight nano-stannic oxide and cuprous oxide by 100：30 ratio
Carry out dry ball milling mixing 1h；Then it places in atmosphere furnace and carries out carbon thermal reduction, be warming up under nitrogen protection with 5 DEG C/min
800 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains stannic oxide modified product.
（2）The compound of stannic oxide modified product and graphite：Stannic oxide modified product is subjected to 400 mesh sievings,
Take its minus mesh with graphite, pitch, phenolic resin in proportion with V-arrangement mixing machine 25Hz mixing 1h, its ratio be graphite：Titanium dioxide
Tin modification product：Pitch：Phenolic resin=100：15：10：5；Mixture is put into moulding press, compound stalk forming is carried out with 18MPa,
Then molding materials are put into firing chamber to roast, is heated up in a nitrogen atmosphere with the speed of 5 DEG C/min since room temperature
600 DEG C are warming up to 150 DEG C, 90 min of constant temperature, then with the speed of 5 DEG C/min, 240 min of constant temperature；It is cooled to room temperature,
It is broken just broken that Hubei Province carried out to molding materials, carries out breaing up shaping subsequently into roll mill, d50 is controlled at 12-14 μm, is tentatively obtained
The compound secondary granulation product of tin carbon.The graphite is high-purity natural spherical graphite, and d50 is 8-10 μm, and the pitch is medium temperature
Pitch, d50 are 4-6 μm, and the d50 of the phenolic resin is 4-6 μm.
（3）Secondary coating modification：By step（2）The compound secondary granulation product of tin carbon obtained presses 100 with hard pitch：5
Ratio V-arrangement mixing machine 25Hz mixing 1h, then place atmosphere furnace in carry out carbon thermal reduction, under nitrogen protection with 5 DEG C/
Min is warming up to 900 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains final secondary coating modification product.
Fig. 1 is the scanning electron microscope (SEM) photograph of the tin-carbon composite product obtained in the present embodiment.Made sample is micro- as shown in Figure 1
Sight pattern is secondary granulation structure, and stannic oxide and partial reduction products are evenly coated at graphite surface.
Fig. 2 is the simulated battery test curve figure of the tin-carbon composite product obtained in the present embodiment（Material gram specific volume
Amount plays 383mAh/g, first charge discharge efficiency 92.6%）.As shown in Figure 2 made sample have apparent tin carbon voltage platform, the 2nd time and
3 times charging and discharging curves overlap preferably, and capacity is without apparent relaxation phenomenon.
Embodiment 2：
A method of tin carbon lithium ion negative material is prepared, includes following steps：
（1）The doping vario-property of stannic oxide：Weigh constant weight nano-stannic oxide and cuprous oxide by 100：10 ratio
Carry out dry ball milling mixing 1h；Then it places in atmosphere furnace and carries out carbon thermal reduction, be warming up under nitrogen protection with 5 DEG C/min
700 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains stannic oxide modified product.
（2）The compound of stannic oxide modified product and graphite：Stannic oxide modified product is subjected to 400 mesh sievings,
Take its minus mesh with graphite, pitch, phenolic resin in proportion with V-arrangement mixing machine 25Hz mixing 1h, its ratio be graphite：Titanium dioxide
Tin modification product：Pitch：Phenolic resin=100：15：5：3；Mixture is put into moulding press, compound stalk forming is carried out with 15MPa,
Then molding materials are put into firing chamber to roast, is heated up in a nitrogen atmosphere with the speed of 5 DEG C/min since room temperature
600 DEG C are warming up to 150 DEG C, 90 min of constant temperature, then with the speed of 5 DEG C/min, 240 min of constant temperature；It is cooled to room temperature,
It is broken just broken that Hubei Province carried out to molding materials, carries out breaing up shaping subsequently into roll mill, d50 is controlled at 12-14 μm, is tentatively obtained
The compound secondary granulation product of tin carbon.The graphite is high-purity natural spherical graphite, and d50 is 8-10 μm, and the pitch is medium temperature
Pitch, d50 are 4-6 μm, and the d50 of the phenolic resin is 4-6 μm.
（3）Secondary coating modification：By step（2）The compound secondary granulation product of tin carbon obtained presses 100 with hard pitch：3
Ratio V-arrangement mixing machine 25Hz mixing 1h, then place atmosphere furnace in carry out carbon thermal reduction, under nitrogen protection with 5 DEG C/
Min is warming up to 800 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains final secondary coating modification product.
After tested, its gram of specific capacity performance 379mAh/g of the product being prepared in the present embodiment, first charge discharge efficiency 91.6%,
And the 2nd time and 3 charging and discharging curves overlap preferable, and capacity is without apparent relaxation phenomenon.
Embodiment 3：
A method of tin carbon lithium ion negative material is prepared, includes following steps：
（1）The doping vario-property of stannic oxide：Weigh constant weight nano-stannic oxide and cuprous oxide by 100：50 ratio
Carry out dry ball milling mixing 1h；Then it places in atmosphere furnace and carries out carbon thermal reduction, be warming up under nitrogen protection with 5 DEG C/min
950 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains stannic oxide modified product.
（2）The compound of stannic oxide modified product and graphite：Stannic oxide modified product is subjected to 400 mesh sievings,
Take its minus mesh with graphite, pitch, phenolic resin in proportion with V-arrangement mixing machine 25Hz mixing 1h, its ratio be graphite：Titanium dioxide
Tin modification product：Pitch：Phenolic resin=100：15：15：12；By mixture be put into moulding press with 19MPa carry out briquetting at
Then type is put molding materials into firing chamber and is roasted, in a nitrogen atmosphere with the speed of 5 DEG C/min since room temperature
150 DEG C, 90 min of constant temperature are warming up to, then 600 DEG C are warming up to the speed of 5 DEG C/min, 240 min of constant temperature；It is cooled to
It is broken just broken to carry out Hubei Province to molding materials, carries out breaing up shaping subsequently into roll mill, d50 is controlled at 12-14 μm, just for room temperature
Step obtains the compound secondary granulation product of tin carbon.The graphite is high-purity natural spherical graphite, and d50 is 8-10 μm, the pitch
For mid temperature pitch, d50 is 4-6 μm, and the d50 of the phenolic resin is 4-6 μm.
（3）Secondary coating modification：By step（2）The compound secondary granulation product of tin carbon obtained presses 100 with hard pitch：8
Ratio V-arrangement mixing machine 25Hz mixing 1h, then place atmosphere furnace in carry out carbon thermal reduction, under nitrogen protection with 5 DEG C/
Min is warming up to 850 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains final secondary coating modification product.
After tested, its gram of specific capacity performance 375mAh/g of the product being prepared in the present embodiment, first charge discharge efficiency 90.8%,
And the 2nd time and 3 charging and discharging curves overlap preferable, and capacity is without apparent relaxation phenomenon.
Embodiment 4：
A method of tin carbon lithium ion negative material is prepared, includes following steps：
（1）The doping vario-property of stannic oxide：Weigh constant weight nano-stannic oxide and cuprous oxide by 100：40 ratio
Carry out dry ball milling mixing 1h；Then it places in atmosphere furnace and carries out carbon thermal reduction, be warming up under nitrogen protection with 5 DEG C/min
850 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains stannic oxide modified product.
（2）The compound of stannic oxide modified product and graphite：Stannic oxide modified product is subjected to 400 mesh sievings,
Take its minus mesh with graphite, pitch, phenolic resin in proportion with V-arrangement mixing machine 25Hz mixing 1h, its ratio be graphite：Titanium dioxide
Tin modification product：Pitch：Phenolic resin=100：15： 20：8；By mixture be put into moulding press with 20MPa carry out briquetting at
Then type is put molding materials into firing chamber and is roasted, in a nitrogen atmosphere with the speed of 5 DEG C/min since room temperature
150 DEG C, 90 min of constant temperature are warming up to, then 600 DEG C are warming up to the speed of 5 DEG C/min, 240 min of constant temperature；It is cooled to
It is broken just broken to carry out Hubei Province to molding materials, carries out breaing up shaping subsequently into roll mill, d50 is controlled at 12-14 μm, just for room temperature
Step obtains the compound secondary granulation product of tin carbon.The graphite is high-purity natural spherical graphite, and d50 is 8-10 μm, the pitch
For mid temperature pitch, d50 is 4-6 μm, and the d50 of the phenolic resin is 4-6 μm.
（3）Secondary coating modification：By step（2）The compound secondary granulation product of tin carbon obtained presses 100 with hard pitch：10
Ratio V-arrangement mixing machine 25Hz mixing 1h, then place atmosphere furnace in carry out carbon thermal reduction, under nitrogen protection with 5 DEG C/
Min is warming up to 950 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains final secondary coating modification product.
After tested, its gram of specific capacity performance 375mAh/g of the product being prepared in the present embodiment, first charge discharge efficiency 91.1%,
And the 2nd time and 3 charging and discharging curves overlap preferable, and capacity is without apparent relaxation phenomenon.
Embodiment 5：
A method of tin carbon lithium ion negative material is prepared, includes following steps：
（1）The doping vario-property of stannic oxide：Weigh constant weight nano-stannic oxide and cuprous oxide by 100：20 ratio
Carry out dry ball milling mixing 1h；Then it places in atmosphere furnace and carries out carbon thermal reduction, be warming up under nitrogen protection with 5 DEG C/min
780 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains stannic oxide modified product.
（2）The compound of stannic oxide modified product and graphite：Stannic oxide modified product is subjected to 400 mesh sievings,
Take its minus mesh with graphite, pitch, phenolic resin in proportion with V-arrangement mixing machine 25Hz mixing 1h, its ratio be graphite：Titanium dioxide
Tin modification product：Pitch：Phenolic resin=100：15：18：10；By mixture be put into moulding press with 16MPa carry out briquetting at
Then type is put molding materials into firing chamber and is roasted, in a nitrogen atmosphere with the speed of 5 DEG C/min since room temperature
150 DEG C, 90 min of constant temperature are warming up to, then 600 DEG C are warming up to the speed of 5 DEG C/min, 240 min of constant temperature；It is cooled to
It is broken just broken to carry out Hubei Province to molding materials, carries out breaing up shaping subsequently into roll mill, d50 is controlled at 12-14 μm, just for room temperature
Step obtains the compound secondary granulation product of tin carbon.The graphite is high-purity natural spherical graphite, and d50 is 8-10 μm, the pitch
For mid temperature pitch, d50 is 4-6 μm, and the d50 of the phenolic resin is 4-6 μm.
（3）Secondary coating modification：By step（2）The compound secondary granulation product of tin carbon obtained presses 100 with hard pitch：4
Ratio V-arrangement mixing machine 25Hz mixing 1h, then place atmosphere furnace in carry out carbon thermal reduction, under nitrogen protection with 5 DEG C/
Min is warming up to 1000 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains final secondary coating modification product.
After tested, its gram of specific capacity performance 374mAh/g of the product being prepared in the present embodiment, first charge discharge efficiency 90.5%,
And the 2nd time and 3 charging and discharging curves overlap preferable, and capacity is without apparent relaxation phenomenon.
Embodiment 6：
A method of tin carbon lithium ion negative material is prepared, includes following steps：
（1）The doping vario-property of stannic oxide：Weigh constant weight nano-stannic oxide and cuprous oxide by 100：25 ratio
Carry out dry ball milling mixing 1h；Then it places in atmosphere furnace and carries out carbon thermal reduction, be warming up under nitrogen protection with 5 DEG C/min
750 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains stannic oxide modified product.
（2）The compound of stannic oxide modified product and graphite：Stannic oxide modified product is subjected to 400 mesh sievings,
Take its minus mesh with graphite, pitch, phenolic resin in proportion with V-arrangement mixing machine 25Hz mixing 1h, its ratio be graphite：Titanium dioxide
Tin modification product：Pitch：Phenolic resin=100：15：8：9；Mixture is put into moulding press, compound stalk forming is carried out with 17MPa,
Then molding materials are put into firing chamber to roast, is heated up in a nitrogen atmosphere with the speed of 5 DEG C/min since room temperature
600 DEG C are warming up to 150 DEG C, 90 min of constant temperature, then with the speed of 5 DEG C/min, 240 min of constant temperature；It is cooled to room temperature,
It is broken just broken that Hubei Province carried out to molding materials, carries out breaing up shaping subsequently into roll mill, d50 is controlled at 12-14 μm, is tentatively obtained
The compound secondary granulation product of tin carbon.The graphite is high-purity natural spherical graphite, and d50 is 8-10 μm, and the pitch is medium temperature
Pitch, d50 are 4-6 μm, and the d50 of the phenolic resin is 4-6 μm.
（3）Secondary coating modification：By step（2）The compound secondary granulation product of tin carbon obtained presses 100 with hard pitch：7
Ratio V-arrangement mixing machine 25Hz mixing 1h, then place atmosphere furnace in carry out carbon thermal reduction, under nitrogen protection with 5 DEG C/
Min is warming up to 1050 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains final secondary coating modification product.
After tested, its gram of specific capacity performance 376mAh/g of the product being prepared in the present embodiment, first charge discharge efficiency 91.4%,
And the 2nd time and 3 charging and discharging curves overlap preferable, and capacity is without apparent relaxation phenomenon.
The design focal point of the present invention is：The present invention is doped modification using cuprous oxide to stannic oxide, reduces
The expansion characteristics of tin carbon complex, improve cycle performance；Using compression molding, roasts and break up shaping process and secondary make
Grain, the time is short, simple for process, easily realizes industrialization large-scale production；Realize stannic oxide and graphite simultaneously, graphite and graphite it
Between the advantages of being granulated, and can realize the function that surface modification is carried out to stannic oxide and graphite；It can be apparent using secondary cladding
Improve the surface defect generated during secondary granulation, promotes the first charge discharge efficiency and cycle performance of product.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore it is every according to the technical essence of the invention to any subtle modifications, equivalent variations and modifications made by above example, still
Belong in the range of technical solution of the present invention.
Claims (4)
1. a kind of method preparing tin carbon lithium ion negative material, it is characterised in that：Include following steps：
（1）The doping vario-property of stannic oxide：Weigh constant weight nano-stannic oxide and cuprous oxide by 100：The ratio of 10-50
Example carries out dry ball milling mixing 1h；Then it places in atmosphere furnace and carries out carbon thermal reduction, be warming up under nitrogen protection with 5 DEG C/min
700-950 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains stannic oxide modified product；
（2）The compound of stannic oxide modified product and graphite：Stannic oxide modified product is subjected to 400 mesh sievings, takes it
Minus mesh is with graphite, pitch, phenolic resin in proportion with V-arrangement mixing machine 25Hz mixing 1h, and its ratio be graphite：Stannic oxide changes
Property product：Pitch：Phenolic resin=100：15：5-20：3-15；Mixture is put into moulding press, briquetting is carried out with 15-20MPa
Molding, then puts molding materials into firing chamber and roasts, in a nitrogen atmosphere with the speed of 5 DEG C/min since room temperature
Degree is warming up to 150 DEG C, 90 min of constant temperature, then is warming up to 600 DEG C with the speed of 5 DEG C/min, 240 min of constant temperature；It is cooling
To room temperature, it is broken just broken that Hubei Province carried out to molding materials, carries out breaing up shaping subsequently into roll mill, d50 is controlled at 12-14 μm,
Tentatively obtain the compound secondary granulation product of tin carbon；
（3）Secondary coating modification：By step（2）The compound secondary granulation product of tin carbon obtained presses 100 with hard pitch：3-10's
Then ratio V-arrangement mixing machine 25Hz mixing 1h are placed in atmosphere furnace and are carried out carbon thermal reduction, under nitrogen protection with 5 DEG C/min
It is warming up to 800-1050 DEG C of constant temperature 2 hours；It is cooled to room temperature, obtains final secondary coating modification product.
2. a kind of method preparing tin carbon lithium ion negative material according to claim 1, it is characterised in that：It is described to state step
Suddenly（2）Graphite is high-purity natural spherical graphite, and d50 is 8-10 μm.
3. a kind of method preparing tin carbon lithium ion negative material according to claim 1, it is characterised in that：The step
（2）Middle pitch is mid temperature pitch, and d50 is 4-6 μm.
4. a kind of method preparing tin carbon lithium ion negative material according to claim 1, it is characterised in that：The step
（2）The d50 of middle phenolic resin is 4-6 μm.
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