CN109148866A - A kind of preparation method of graphene doped alloys lithium cell cathode material - Google Patents
A kind of preparation method of graphene doped alloys lithium cell cathode material Download PDFInfo
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- CN109148866A CN109148866A CN201811047775.9A CN201811047775A CN109148866A CN 109148866 A CN109148866 A CN 109148866A CN 201811047775 A CN201811047775 A CN 201811047775A CN 109148866 A CN109148866 A CN 109148866A
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses a kind of preparation methods of graphene doped alloys lithium cell cathode material, the preparation method comprises the following steps: (1) by graphene, alloy, LiFePO4 carries out ingredient according to certain mol proportion, it is uniformly mixed, ball milling 12~for 24 hours is carried out under inert atmosphere protection, temperature of charge in ball mill is controlled at 30~40 DEG C, obtain the mixed material that partial size is 10~30nm, wherein, the graphene, the alloy, the molar ratio of the LiFePO4 is 0.4~0.5:0.1~0.3:1, the alloy includes: 5~10 parts of lithium in parts by weight, 15~20 parts of tin, 25~40 parts of nickel, 0~3 part of impurity；(2) cooling in 800~900 DEG C of 5~15h of calcining at constant temperature by the mixed material in step (1) under inert atmosphere protection, it is packed into mold, the compression moulding on hydraulic press obtains graphene doped alloys lithium cell cathode material.Present invention process is simple, and obtained graphene doped alloys lithium cell cathode material has the advantages that charge-discharge performance is good, good cycling stability.
Description
Technical field
The present invention relates to lithium battery material technical fields, more particularly to a kind of graphene doped alloys lithium ion battery anode material
The preparation method of material.
Background technique
Lithium ion battery is light-weight because it is with small in size, and voltage is high, and self discharge is small, good rate capability, environmental-friendly,
The advantages that specific energy is high and be widely applied.Currently it is mainly used in mobile electronic device, national defense industry, electric car etc.
Field.Electrode material is the core of lithium ion battery, and determines the key factor of performance of lithium ion battery.Currently, passing
The graphite cathode material theoretical specific capacity of system is 372mAh/g, has been unable to meet height ratio capacity graphene doped alloys lithium of new generation
The demand of cell negative electrode material.The alloy theoretical capacity with higher formed by bimetallic and cheaper cost etc. are excellent
Point is expected to become ideal graphene doped alloys lithium cell cathode material.
But alloy volume change when lithium ion is embedded in is very big, causes its capacity attenuation fast, high rate performance
Difference, the practical application that this disadvantage limits them in lithium ion battery.Pass through the design and optimization of synthesis route, structure
The transition metal oxide combination electrode material with special construction and pattern is produced, excellent electrochemistry can be made it have
Energy.
For this reason, it is necessary in view of the above-mentioned problems, propose a kind of preparation side of graphene doped alloys lithium cell cathode material
Method is able to solve problems of the prior art.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of graphene doped alloys lithium cell cathode material, to overcome
Deficiency in the prior art.
To achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of graphene doped alloys lithium cell cathode material, the preparation method comprises the following steps:
(1) graphene, alloy, LiFePO4 are subjected to ingredient according to certain mol proportion, are uniformly mixed, protected in inert atmosphere
The lower progress ball milling 12 of shield~for 24 hours, the temperature of charge in ball mill controls the mixing for obtaining that partial size is 10~30nm at 30~40 DEG C
Material, wherein the graphene, the alloy, the LiFePO4 molar ratio be 0.4~0.5:0.1~0.3:1, it is described
Alloy includes: 5~10 parts of lithium, 15~20 parts of tin, 25~40 parts of nickel, 0~3 part of impurity in parts by weight；
(2) by the mixed material in step (1) under inert atmosphere protection, in 800~900 DEG C of 5~15h of calcining at constant temperature,
It is cooling, it is packed into mold, the compression moulding on hydraulic press obtains graphene doped alloys lithium cell cathode material.
Preferably, in above-mentioned steps (1), the graphene, the alloy, the LiFePO4 molar ratio be 0.45:
0.2:1。
Preferably, in above-mentioned steps (1), the alloy includes: 7.5 parts of lithium in parts by weight, and 18 parts of tin, 32 parts of nickel,
1.5 parts of impurity.
Preferably, in above-mentioned steps (1), the partial size of the mixed material is 20nm.
Preferably, in above-mentioned steps (1), the impurity is titanium, cobalt, manganese, iron, any number of mixing of aluminium, boron.
Preferably, in above-mentioned steps (1) and step (2), the inert atmosphere is nitrogen atmosphere or argon atmosphere.
Preferably, in above-mentioned steps (2), the pressure in pressing process is 1~10MPa.
Preferably, in above-mentioned steps (2), compacting with a thickness of 0.1~1mm.
Compared with the prior art, the advantages of the present invention are as follows: present invention process is simple, obtained graphene doped alloys
Lithium cell cathode material has the advantages that charge-discharge performance is good, good cycling stability.
Specific embodiment
The present invention is described further by the following example: according to following embodiments, the present invention may be better understood.
However, as it will be easily appreciated by one skilled in the art that specific material ratio, process conditions and its result described in embodiment are only used
In illustrating the present invention, without the present invention described in detail in claims should will not be limited.
The present invention discloses a kind of preparation method of graphene doped alloys lithium cell cathode material, and the preparation method includes
Following steps:
(1) graphene, alloy, LiFePO4 are subjected to ingredient according to certain mol proportion, are uniformly mixed, protected in inert atmosphere
The lower progress ball milling 12 of shield~for 24 hours, the temperature of charge in ball mill controls the mixing for obtaining that partial size is 10~30nm at 30~40 DEG C
Material, wherein the graphene, the alloy, the LiFePO4 molar ratio be 0.4~0.5:0.1~0.3:1, it is described
Alloy includes: 5~10 parts of lithium, 15~20 parts of tin, 25~40 parts of nickel, 0~3 part of impurity in parts by weight；
(2) by the mixed material in step (1) under inert atmosphere protection, in 800~900 DEG C of 5~15h of calcining at constant temperature,
It is cooling, it is packed into mold, the compression moulding on hydraulic press obtains graphene doped alloys lithium cell cathode material.
In above-mentioned steps (1), the graphene, the alloy, the LiFePO4 molar ratio be 0.45:0.2:1；Institute
Stating alloy in parts by weight includes: 7.5 parts of lithium, 18 parts of tin, 32 parts of nickel, 1.5 parts of impurity；Wherein, the impurity be titanium, cobalt,
Manganese, iron, any number of mixing of aluminium, boron；The partial size of the mixed material is 20nm.
In above-mentioned steps (2), pressure in pressing process is 1~10MPa, it is preferred that the pressure in pressing process is
5MPa；Compacting with a thickness of 0.1~1mm, it is preferred that compacting with a thickness of 0.5mm.
In above-mentioned steps (1) and step (2), the inert atmosphere is nitrogen atmosphere or argon atmosphere.
It is following to be illustrated with specifically embodiment, to prepare the graphene doped alloys lithium ion battery anode material in the present invention
Material.
Embodiment 1
(1) graphene, alloy, LiFePO4 are subjected to ingredient according to certain mol proportion, are uniformly mixed, protected in inert atmosphere
Shield is lower to carry out ball milling 12h, and the temperature of charge in ball mill controls the mixed material for obtaining that partial size is 10nm at 30 DEG C, wherein institute
State graphene, the alloy, the LiFePO4 molar ratio be 0.4:0.1:1, the alloy includes: lithium in parts by weight
5 parts, 15 parts of tin, 25 parts of nickel, 0 part of impurity；
(2) cooling in 800 DEG C of calcining at constant temperature 5h by the mixed material in step (1) under inert atmosphere protection, it is packed into
Mold, the compression moulding on the hydraulic press that pressure is 1Mpa, compacting with a thickness of 0.1mm, obtain graphene doped alloys lithium electricity
Pond negative electrode material.
Embodiment 2
(1) graphene, alloy, LiFePO4 are subjected to ingredient according to certain mol proportion, are uniformly mixed, protected in inert atmosphere
Shield is lower to carry out ball milling 18h, and the temperature of charge in ball mill controls the mixed material for obtaining that partial size is 20nm at 35 DEG C, wherein institute
State graphene, the alloy, the LiFePO4 molar ratio be 0.45:0.2:1, the alloy includes: in parts by weight
7.5 parts of lithium, 18 parts of tin, 32 parts of nickel, 1.5 parts of impurity；
(2) cooling in 850 DEG C of calcining at constant temperature 10h by the mixed material in step (1) under inert atmosphere protection, it is packed into
Mold, the compression moulding on the hydraulic press that pressure is 5Mpa, compacting with a thickness of 0.5mm, obtain graphene doped alloys lithium electricity
Pond negative electrode material.
Embodiment 3
(1) graphene, alloy, LiFePO4 are subjected to ingredient according to certain mol proportion, are uniformly mixed, protected in inert atmosphere
Shield is lower to carry out ball milling for 24 hours, and the temperature of charge in ball mill controls the mixed material for obtaining that partial size is 30nm at 40 DEG C, wherein institute
State graphene, the alloy, the LiFePO4 molar ratio be 0.5:0.3:1, the alloy includes: lithium in parts by weight
10 parts, 20 parts of tin, 40 parts of nickel, 3 parts of impurity；
(2) cooling in 900 DEG C of calcining at constant temperature 15h by the mixed material in step (1) under inert atmosphere protection, it is packed into
Mold, pressure be 10Mpa hydraulic press on compression moulding, compacting with a thickness of 1mm, obtain graphene doped alloys lithium battery
Negative electrode material.
By XRD, SEM, electro-chemical test to the graphene doped alloys lithium electricity being prepared in above-described embodiment 1~3
Pond negative electrode material is tested, the results showed that, the grain size of the graphene doped alloys lithium cell cathode material is 10~
30nm；Discharge capacity reaches 486mAh/g for the first time for it, and charging capacity reaches 352mAh/g, decays to initial capacity after 500 circle of circulation
85.6%~91.5%.
Finally, it is to be noted that, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive
Property include so that include a series of elements process, method, article or equipment not only include those elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Element.
Claims (8)
1. a kind of preparation method of graphene doped alloys lithium cell cathode material, which is characterized in that the preparation method includes
Following steps:
(1) graphene, alloy, LiFePO4 are subjected to ingredient according to certain mol proportion, are uniformly mixed, under inert atmosphere protection
Progress ball milling 12~for 24 hours, the temperature of charge in ball mill controls the mixture for obtaining that partial size is 10~30nm at 30~40 DEG C
Material, wherein the graphene, the alloy, the LiFePO4 molar ratio be 0.4~0.5:0.1~0.3:1, the conjunction
Gold includes: 5~10 parts of lithium, 15~20 parts of tin, 25~40 parts of nickel, 0~3 part of impurity in parts by weight；
It is (2) cooling in 800~900 DEG C of 5~15h of calcining at constant temperature by the mixed material in step (1) under inert atmosphere protection,
It is packed into mold, the compression moulding on hydraulic press obtains graphene doped alloys lithium cell cathode material.
2. the preparation method of graphene doped alloys lithium cell cathode material according to claim 1, which is characterized in that on
State in step (1), the graphene, the alloy, the LiFePO4 molar ratio be 0.45:0.2:1.
3. the preparation method of graphene doped alloys lithium cell cathode material according to claim 1, which is characterized in that on
It states in step (1), the alloy includes: 7.5 parts of lithium, 18 parts of tin, 32 parts of nickel, 1.5 parts of impurity in parts by weight.
4. the preparation method of graphene doped alloys lithium cell cathode material according to claim 1, which is characterized in that on
It states in step (1), the partial size of the mixed material is 20nm.
5. the preparation method of graphene doped alloys lithium cell cathode material according to claim 1, which is characterized in that on
It states in step (1), the impurity is titanium, cobalt, manganese, iron, any number of mixing of aluminium, boron.
6. the preparation method of graphene doped alloys lithium cell cathode material according to claim 1, which is characterized in that on
It states in step (1) and step (2), the inert atmosphere is nitrogen atmosphere or argon atmosphere.
7. the preparation method of graphene doped alloys lithium cell cathode material according to claim 1, which is characterized in that on
It states in step (2), the pressure in pressing process is 1~10MPa.
8. the preparation method of graphene doped alloys lithium cell cathode material according to claim 1, which is characterized in that on
State in step (2), compacting with a thickness of 0.1~1mm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110311108A (en) * | 2019-06-28 | 2019-10-08 | 徐州硕祥信息科技有限公司 | A kind of preparation method of low self-discharge lithium cell cathode material |
| CN110797531A (en) * | 2019-10-11 | 2020-02-14 | 合肥国轩高科动力能源有限公司 | Microwave-grafting graphene treatment method and modification method for improving high-rate discharge performance of lithium iron phosphate by using same |
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| US20130323607A1 (en) * | 2009-11-24 | 2013-12-05 | Nikolai Nikolaevich Issaev | Secondary electrochemical cells with separator and electrolyte combination |
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2018
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Patent Citations (3)
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| US20130323607A1 (en) * | 2009-11-24 | 2013-12-05 | Nikolai Nikolaevich Issaev | Secondary electrochemical cells with separator and electrolyte combination |
| CN101752561A (en) * | 2009-12-11 | 2010-06-23 | 中国科学院宁波材料技术与工程研究所 | Graphite alkene iron lithium phosphate positive active material, preparing method thereof, and lithium ion twice battery based on the graphite alkene modified iron lithium phosphate positive active material |
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Non-Patent Citations (1)
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| XIAOYUAN ZENG: "Electrochemical Behavior of Spherical LiFePO4/C Nanomaterial in Aqueous Electrolyte, and Novel Aqueous Rechargeable Lithium Battery with LiFePO4/C anode", 《ELECTROCHIMICA ACTA》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110311108A (en) * | 2019-06-28 | 2019-10-08 | 徐州硕祥信息科技有限公司 | A kind of preparation method of low self-discharge lithium cell cathode material |
| CN110797531A (en) * | 2019-10-11 | 2020-02-14 | 合肥国轩高科动力能源有限公司 | Microwave-grafting graphene treatment method and modification method for improving high-rate discharge performance of lithium iron phosphate by using same |
| CN110797531B (en) * | 2019-10-11 | 2022-04-12 | 合肥国轩高科动力能源有限公司 | Microwave-grafting graphene treatment method and modification method for improving high-rate discharge performance of lithium iron phosphate by using same |
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