CN105789588A - Preparation method of multilayer structure battery cathode material containing C3N4 composite material - Google Patents
Preparation method of multilayer structure battery cathode material containing C3N4 composite material Download PDFInfo
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- CN105789588A CN105789588A CN201610208924.XA CN201610208924A CN105789588A CN 105789588 A CN105789588 A CN 105789588A CN 201610208924 A CN201610208924 A CN 201610208924A CN 105789588 A CN105789588 A CN 105789588A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a multilayer structure battery cathode material containing a C3N4 composite material. By adopting the method, a complete carbon layer structure generates lots of defects and active sites which can better capture lithium ions so as to increase the lithium insertion quantity and improve the specific capacity of the cathode material; moreover, a rough-surface copper-plated aluminum foil is selected in structure and has the advantage of large specific surface area, and the relatively large specific surface area and a concave-convex structure can perfectly buffer the volume expansion in the charge/discharge process of tin; and meanwhile, the structure also can perfectly play a role of a skeleton, and the stress of volume expansion/shrinkage in the charge/discharge process is greatly buffered so as to improve the cycle performance of the aluminum/copper/tin/graphite multilayer structure cathode material.
Description
Technical field
The present invention relates to a kind of containing C3N4The preparation method of the multiple structure cell negative electrode material of composite.
Background technology
Lithium ion battery is mainly made up of shell, positive pole, negative pole, electrolyte and barrier film, and wherein negative material is mainly material with carbon element.Current business-like lithium ion battery negative material has graphite-like carbon, easy graphitized carbon (soft carbon), amorphous carbon (hard carbon) material three major types, but the theoretical specific capacity of graphite only has 372mAh/g, and manufacturing cost is high, poor safety performance；Though soft material with carbon element has substantial amounts of Turbostratic and heteroatom such as hydrogen etc. so that it is having higher specific capacity (being typically in 600-800mAh/g), but its voltage delay is big, initial coulomb efficiency is low, and it is very fast to decay, and therefore practical application is extremely restricted；Compared with soft material with carbon element, the platform of hard carbon material is relatively low, and efficiency and cycle life are all improved first, but specific capacity is lower than soft material with carbon element.
Summary of the invention
The present invention provides a kind of containing C3N4The preparation method of the multiple structure cell negative electrode material of composite, the negative material using the method to prepare, there is high connductivity, high rate capability and long circulating performance.
To achieve these goals, the present invention provides a kind of containing C3N4The preparation method of the multiple structure cell negative electrode material of composite, the method comprises the steps:
(1) C/C is prepared3N4Composite
By condensed-nuclei aromatics compound and organic compounds containing nitrogen according to mol ratio 1:(0.5-5) after Homogeneous phase mixing, it is placed in autoclave, described condensed-nuclei aromatics compound is: naphthalene, anthracene, pyrene, medium temperature coal pitch, one or more in petroleum residual oil Colophonium；Organic compounds containing nitrogen is: carbamide, hexamethylenetetramine, one or more in tripolycyanamide；
With the air in nitrogen replacement reaction kettle, controlling reactor initial pressure is 0-2Mpa；
By the reactor heating rate according to 5 DEG C/min, it is warming up to 400-600 DEG C；
The isothermal reaction time controls at 3-6 hour, takes out product after having reacted；
Unreacted raw material is washed away with chloroform, sucking filtration is carried out with film filter, when washing reaction product, product should be mixed in the ratio of 1g:50mL solvent, and magnetic agitation is after 3 hours, carry out sucking filtration with film filter again, the product overclocking oscillator obtained is ground to particle diameter less than 200 orders, obtains C/C3N4Composite；
(2) aluminium foil being carried out pretreatment: be sequentially carried out electrochemical deoiling, acid etching, once heavy zinc at aluminium foil surface, move back zinc, the heavy zinc of secondary and washing, the thickness of described aluminium foil is 15-20 μm；
One layer of copper coating of aluminium foil side electroplating surface after the pre-treatment also activates, and copper coating adopts pulse plating regime plating, and its surface roughness is 0.4-3.0 μm, and thickness is 2-8 μm；
Copper coating after activation is electroplated one layer of tin coating；
The C/C obtained on being coated with one layer on described tin coating3N4Composite, C/C3N4The thickness of composite layer is 80-150 μm；
(3) heat treatment: temperature is 80-100 DEG C, heat treatment time is 12-20 hour.
Preferably, the thickness of described tin coating is 0.1-1.0 μm, and electrotinning coating adopts the tin plating formula of impulse jet plating and technological parameter as follows:
Impulse jet electroplating technological parameter: electric current density: 5-15A/dm2；
PH value: 3-4；
Temperature: 45-55 DEG C；
Time: 5-20s.
The C of the present invention3N4The existence of structure, makes complete carbon-coating structure create substantial amounts of defect and avtive spot on the one hand, and these defects and avtive spot can catch lithium ion better, thus improving lithium-inserting amount, therefore the specific capacity of negative material is promoted；On the other hand, nitrogen element can change the electron cloud arrangement in carbon-coating around carbon atom so that it is possesses more excellent electric conductivity and chemical property, thus improving high rate performance and the cycle performance of negative material.Structure has been selected a kind of rough surface copper facing aluminium foil, this copper facing aluminium foil has the advantage that specific surface area is big, bigger specific surface area and concaveconvex structure can well cushion stannum volumetric expansion in charge and discharge process, this structure also acts as good skeleton function simultaneously, the stress that in buffering charge and discharge process, volumetric expansion is shunk greatly.Negative material first charge-discharge efficiency is 77%, discharges with 400mA/g, circulates 360 weeks, and capability retention is 78%, discharges with 600mA/g, circulates 480 weeks, and capability retention is 89%.This inventive method technique is simple, easy to control, is suitable for large-scale production.
Detailed description of the invention
Embodiment one
By condensed-nuclei aromatics compound and organic compounds containing nitrogen according to, after mol ratio 1:0.5 Homogeneous phase mixing, being placed in autoclave, described condensed-nuclei aromatics compound is: naphthalene, anthracene, pyrene, medium temperature coal pitch, one or more in petroleum residual oil Colophonium；Organic compounds containing nitrogen is: carbamide, hexamethylenetetramine, one or more of tripolycyanamide.
With the air in nitrogen replacement reaction kettle, controlling reactor initial pressure is 0-2Mpa；
By the reactor heating rate according to 5 DEG C/min, it is warming up to 400 DEG C；
The isothermal reaction time controls at 3 hours, takes out product after having reacted；
Unreacted raw material is washed away with chloroform, sucking filtration is carried out with film filter, when washing reaction product, product should be mixed in the ratio of 1g:50mL solvent, and magnetic agitation is after 3 hours, carry out sucking filtration with film filter again, the product overclocking oscillator obtained is ground to particle diameter less than 200 orders, obtains C/C3N4Composite.
Aluminium foil being carried out pretreatment: be sequentially carried out electrochemical deoiling, acid etching, once heavy zinc at aluminium foil surface, move back zinc, the heavy zinc of secondary and washing, the thickness of described aluminium foil is 15 μm；
One layer of copper coating of aluminium foil side electroplating surface after the pre-treatment also activates, and copper coating adopts pulse plating regime plating, and its surface roughness is 0.4 μm, and thickness is 2 μm；
Copper coating after activation is electroplated one layer of tin coating；
The C/C obtained on being coated with one layer on described tin coating3N4Composite, C/C3N4The thickness of composite layer is 80 μm.
The thickness of described tin coating is 0.1 μm, and electrotinning coating adopts the tin plating formula of impulse jet plating and technological parameter as follows:
Impulse jet electroplating technological parameter: electric current density: 5A/dm2；
PH value: 3-4；
Temperature: 45 DEG C；
Time: 5s.
Carrying out heat treatment, heat treatment temperature is 80 DEG C, and heat treatment time is 12 hours.
Embodiment two
By condensed-nuclei aromatics compound and organic compounds containing nitrogen according to, after mol ratio 1:5 Homogeneous phase mixing, being placed in autoclave, described condensed-nuclei aromatics compound is: naphthalene, anthracene, pyrene, one or more in medium temperature coal pitch, petroleum residual oil Colophonium；Organic compounds containing nitrogen is: carbamide, hexamethylenetetramine, one or more in tripolycyanamide；
With the air in nitrogen replacement reaction kettle, controlling reactor initial pressure is 0-2Mpa；
By the reactor heating rate according to 5 DEG C/min, it is warming up to 600 DEG C；
The isothermal reaction time controls at 6 hours, takes out product after having reacted；
Unreacted raw material is washed away with chloroform, sucking filtration is carried out with film filter, when washing reaction product, product should be mixed in the ratio of 1g:50mL solvent, and magnetic agitation is after 3 hours, carry out sucking filtration with film filter again, the product overclocking oscillator obtained is ground to particle diameter less than 200 orders, obtains C/C3N4Composite.
Aluminium foil being carried out pretreatment: be sequentially carried out electrochemical deoiling, acid etching, once heavy zinc at aluminium foil surface, move back zinc, the heavy zinc of secondary and washing, the thickness of described aluminium foil is 20 μm；
One layer of copper coating of aluminium foil side electroplating surface after the pre-treatment also activates, and copper coating adopts pulse plating regime plating, and its surface roughness is 3.0 μm, and thickness is 8 μm；
Copper coating after activation is electroplated one layer of tin coating；
The C/C obtained on being coated with one layer on described tin coating3N4Composite, C/C3N4The thickness of composite layer is 150 μm.
The thickness of described tin coating is 1.0 μm, and electrotinning coating adopts the tin plating formula of impulse jet plating and technological parameter as follows:
Impulse jet electroplating technological parameter: electric current density: 15A/dm2；
PH value: 3-4；
Temperature: 55 DEG C；
Time: 20s.
Carrying out heat treatment, temperature is 100 DEG C, and heat treatment time is 20 hours.
The present invention is described by embodiment, but do not limit the invention, with reference to description of the invention, other changes of the disclosed embodiments, as the professional person for this area is readily apparent that, such change should belong within the scope that the claims in the present invention limit.
Claims (2)
1. one kind containing C3N4The preparation method of the multiple structure cell negative electrode material of composite, the method comprises the steps:
(1) C/C is prepared3N4Composite
By condensed-nuclei aromatics compound and organic compounds containing nitrogen according to mol ratio 1:(0.5-5) after Homogeneous phase mixing, it is placed in autoclave, described condensed-nuclei aromatics compound is: naphthalene, anthracene, pyrene, medium temperature coal pitch, one or more in petroleum residual oil Colophonium；Organic compounds containing nitrogen is: carbamide, hexamethylenetetramine, one or more in tripolycyanamide；
With the air in nitrogen replacement reaction kettle, controlling reactor initial pressure is 0-2Mpa；
By the reactor heating rate according to 5 DEG C/min, it is warming up to 400-600 DEG C；
The isothermal reaction time controls at 3-6 hour, takes out product after having reacted；
Unreacted raw material is washed away with chloroform, sucking filtration is carried out with film filter, when washing reaction product, product should be mixed in the ratio of 1g:50mL solvent, and magnetic agitation is after 3 hours, carry out sucking filtration with film filter again, the product overclocking oscillator obtained is ground to particle diameter less than 200 orders, obtains C/C3N4Composite；
(2) aluminium foil being carried out pretreatment: be sequentially carried out electrochemical deoiling, acid etching, once heavy zinc at aluminium foil surface, move back zinc, the heavy zinc of secondary and washing, the thickness of described aluminium foil is 15-20 μm；
One layer of copper coating of aluminium foil side electroplating surface after the pre-treatment also activates, and copper coating adopts pulse plating regime plating, and its surface roughness is 0.4-3.0 μm, and thickness is 2-8 μm；
Copper coating after activation is electroplated one layer of tin coating；
The C/C obtained on being coated with one layer on described tin coating3N4Composite, C/C3N4The thickness of composite layer is 80-150 μm；
(3) heat treatment: temperature is 80-100 DEG C, heat treatment time is 12-20 hour.
2. the method for claim 1, it is characterised in that the thickness of described tin coating is 0.1-1.0 μm, electrotinning coating adopts the tin plating formula of impulse jet plating and technological parameter as follows:
Impulse jet electroplating technological parameter: electric current density: 5-15A/dm2；
PH value: 3-4；
Temperature: 45-55 DEG C；
Time: 5-20s.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554452A (en) * | 2018-04-11 | 2018-09-21 | 济南大学 | A method of by urea controllable preparation two dimension Organic Carbon And Total Nitrogen |
| CN108620133A (en) * | 2018-05-03 | 2018-10-09 | 同济大学 | A kind of preparation method and applications of the visible light-responded catalysis production hydrogen material of two-dimensional transversal polymer hetero-junctions |
| CN109524639A (en) * | 2018-10-16 | 2019-03-26 | 华南师范大学 | Lithium ion battery g-C is prepared using electrostatic spinning3N4The method and its application of/silicon-carbon cathode material |
| CN109594100A (en) * | 2018-12-07 | 2019-04-09 | 东华大学 | A kind of C3N4Loaded Cu/Sn alloy material and its preparation and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985875A (en) * | 2014-05-21 | 2014-08-13 | 南京理工大学 | Application of graphene-carbon nitride composite material |
| CN105449180A (en) * | 2015-12-30 | 2016-03-30 | 湘潭大学 | Aluminum/copper/tin/graphite multilayer structure lithium ion battery cathode material and preparation method thereof |
-
2016
- 2016-04-06 CN CN201610208924.XA patent/CN105789588A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985875A (en) * | 2014-05-21 | 2014-08-13 | 南京理工大学 | Application of graphene-carbon nitride composite material |
| CN105449180A (en) * | 2015-12-30 | 2016-03-30 | 湘潭大学 | Aluminum/copper/tin/graphite multilayer structure lithium ion battery cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨晓晖 等: ""石墨型C3N4的固态合成及嵌锂性能研究"", 《化学学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554452A (en) * | 2018-04-11 | 2018-09-21 | 济南大学 | A method of by urea controllable preparation two dimension Organic Carbon And Total Nitrogen |
| CN108554452B (en) * | 2018-04-11 | 2021-04-02 | 济南大学 | Method for controllably preparing two-dimensional organic carbon nitrogen from urea |
| CN108620133A (en) * | 2018-05-03 | 2018-10-09 | 同济大学 | A kind of preparation method and applications of the visible light-responded catalysis production hydrogen material of two-dimensional transversal polymer hetero-junctions |
| CN108620133B (en) * | 2018-05-03 | 2020-10-30 | 同济大学 | Preparation method and application of two-dimensional transverse polymer heterojunction visible light response catalytic hydrogen production material |
| CN109524639A (en) * | 2018-10-16 | 2019-03-26 | 华南师范大学 | Lithium ion battery g-C is prepared using electrostatic spinning3N4The method and its application of/silicon-carbon cathode material |
| CN109524639B (en) * | 2018-10-16 | 2020-05-19 | 华南师范大学 | Preparation of lithium ion battery g-C by electrostatic spinning3N4Method for preparing silicon-carbon negative electrode material and application thereof |
| CN109594100A (en) * | 2018-12-07 | 2019-04-09 | 东华大学 | A kind of C3N4Loaded Cu/Sn alloy material and its preparation and application |
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