CN109616639A - A kind of hard carbon cladding expansion microcrystalline graphite material and preparation method thereof and the application in sodium-ion battery - Google Patents
A kind of hard carbon cladding expansion microcrystalline graphite material and preparation method thereof and the application in sodium-ion battery Download PDFInfo
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Abstract
The invention discloses a kind of hard carbons to coat expansion microcrystalline graphite material and preparation method thereof and the application in sodium-ion battery.Hard carbon cladding expansion micro crystal graphite coats expansion micro crystal graphite by hard carbon layer and constitutes.Its preparation process are as follows: after micro crystal graphite ball milling, by chemical graft processing and expansion process, obtain expansion micro crystal graphite；Expand micro crystal graphite using resin carbon source cladding after, carry out carbonization treatment to get.The conductivity of composite material is good, it is high to store up sodium ability, stable structure, it is used to prepare sodium-ion battery as negative electrode material, show height ratio capacity, good high rate performance and long circulating stability energy, and the raw material that composite material preparation process uses is cheap, with short production cycle, has apparent economic benefit, it is easy to accomplish industrial applications.
Description
Technical field
The present invention relates to a kind of anode material of lithium-ion battery, in particular to a kind of low graphitization hard carbon coats high graphitization
Expansion microcrystalline graphite material and preparation method thereof, further relate to hard carbon cladding expansion microcrystalline graphite material as sodium ion Carbon anode
The application of material belongs to secondary cell field.
Background technique
With the development of society, abundant and population the continuous growth of substance, demand of the people to the energy increasingly increases severely.
The conventional fossil fuel that people rely on has when in use to the pollution of environment and non-renewable, therefore to renewable energy
The exploration and use in source (water power, wind energy, solar energy, tide energy, underground heat etc.) become a kind of inexorable trend.It is extensive in new energy
During ground development and utilization, effective storage of energy will be an essential regulation link.Energy storage industry is by the U.S., day
This grade Main Developed Countries are supported as strategic project, and high power density, high-energy density, environmental-friendly, safety is cheap
The research and development of energy storage system have become a research hotspot of current scientific research.
The advantages such as lithium ion battery is high by capacity, operating voltage is high and has extended cycle life occupy the leading of energy storage system
Status, but remain lithium resource shortage and it is expensive the problems such as, therefore develop alternative lithium ion battery and be used for
The energy storage system of extensive energy storage is extremely urgent.Lithium and sodium belong to same main group, have similar physicochemical properties, sodium is on ground
Reserves very abundant in shell, cost is very cheap, therefore sodium-ion battery is considered a kind of with applications well prospect
Electrochemical energy storage system.
Electrode material is the important component of sodium-ion battery, decides the chemical property of battery.To negative electrode material
For, the radius for being limited by sodium ion is big, the problems such as dendrite is easily formed under low potential, and the research of anode material of lithium-ion battery is still
It is so in laboratory stage, the negative electrode material of commercialization urgently researchs and develops.At present, it has been reported that sodium-ion battery cathode material
Material mainly has metal simple-substance and alloy, transistion metal compound, organic matter and carbon based negative electrodes material etc., however in lithium ion battery
In most widely used graphite material be rarely reported, the radius this is mainly due to the radius of sodium ion (0.97nm) than lithium ion
(0.68nm) is bigger, so that sodium ion is difficult to carry out effective deintercalation in graphite material, and graphite is difficult to form stabilization with sodium
The embedding sodium compound of graphite, so graphite material be not suitable for storage sodium.
Summary of the invention
Existing graphite for anode material of lithium-ion battery there are aiming at the problem that, the first purpose of this invention is to be
There is provided it is a kind of the composite material that constitutes of high graphitization expansion micro crystal graphite surface is coated on by one layer of low degree of graphitization hard carbon, should
Composite material is provided simultaneously with the advantages that high activity site, good electric conductivity, stable structure and high-tap density, can be applied to sodium
Ion battery cathode material.
Another object of the present invention be to provide a kind of simple process, it is reproducible, low in cost, environmental-friendly,
It is suitble to the method for preparing a kind of above-mentioned hard carbon cladding expansion microcrystalline graphite material of large-scale production.
Third object of the present invention is to be to provide a kind of application of hard carbon cladding expansion microcrystalline graphite material, is had
The features such as high activity site, good electric conductivity and stable structure, shows high specific volume as sodium-ion battery cathode
Amount, good high rate performance and long circulating stability energy.
In order to achieve the above technical purposes, the present invention provides a kind of hard carbons to coat expansion microcrystalline graphite material, by hard
Carbon-coating cladding expansion micro crystal graphite is constituted.
Hard carbon cladding expansion microcrystalline graphite material proposed by the present invention is primarily directed to micro crystal graphite conduct in the prior art
The improvement project that technical problem present in anode material of lithium-ion battery application process is made.Existing micro crystal graphite has low
Storage sodium and deintercalation ability, it is easy to during sodium ion deintercalation structure destroy, show poor circulation.Present invention design
A kind of completely new complex carbon material out, complex carbon material have core-shell structure, and kernel is the expansion micro crystal graphite of high graphitization,
Outer layer is low graphited hard carbon, has been provided simultaneously with existing low graphitization hard carbon and high graphitization expands the dual excellent of micro crystal graphite
Point；And interior swelling of nucleus micro crystal graphite is the structure of cotton-shaped micro crystal graphite, is more advantageous to the storage of interelectric conduction and sodium ion,
It can be improved the high rate performance of material；And the low graphited hard carbon of outer layer can alleviate lithium ion and be embedded in and take off between micro crystal graphite
Volume expansion problem during out, improves the cyclical stability of graphite material；Spherical housing can increase microlite simultaneously
The tap density of ink, helps to improve the capacity of full battery.Therefore, hard carbon cladding expansion micro crystal graphite realizes sodium-ion battery
The perfect combination of negative electrode material height ratio capacity, high rate capability and high circulation performance.
Hard carbon cladding expansion micro crystal graphite proposed by the present invention has typical core-shell structure, and kernel is extruding microlite
Ink, degree of graphitization is high, good conductivity, and outer layer hard carbon stable structure, provides safeguard for the stability of composite material, and entire
The specific surface area of composite material is moderate, and active site is more.
Preferred scheme, the hard carbon layer with a thickness of 5~50nm, the partial size of hard carbon cladding expansion microcrystalline graphite material is
200~5000nm.
The specific surface area of preferred scheme, hard carbon cladding expansion microcrystalline graphite material is 2~100m2/g。
The present invention also provides the preparation methods that a kind of hard carbon coats expansion microcrystalline graphite material comprising following steps:
1) by micro crystal graphite ball-milling treatment, micro crystal graphite powder is obtained；
2) by micro crystal graphite powder after chemical graft is handled, expansion process is carried out, obtains expansion micro crystal graphite；
3) after the expansion micro crystal graphite is using resin carbon source cladding, it is micro- to get hard carbon cladding expansion to carry out carbonization treatment
Brilliant graphite composite material.
Preferred scheme, the condition of the ball milling are as follows: Ball-milling Time is 4~8 hours, 300~600r/min of revolving speed, ball material
Mass ratio is 20~40:1.
Preferred scheme, the chemical graft processing use the concentrated sulfuric acid for intercalator, and hydrogen peroxide is oxidant.Specific chemistry
Specific step is as follows for intercalation processing: the concentrated sulfuric acid and micro crystal graphite are mixed evenly by liquid-solid ratio for 20~50:1L/kg；
It is that hydrogen peroxide is added in 1:10~30g/mL by the mass volume ratio of the micro crystal graphite and hydrogen peroxide, to stir evenly at room temperature
Afterwards, 60 DEG C are warming up to continue to stir 2h；Deionized water is added, is warming up to 100 DEG C and continues to stir 2h；By resulting mixed solution into
Then row vacuum filter is washed and is dried to filtrate, micro crystal graphite can must be expanded.
Preferred scheme, the temperature of the expansion process are 400~500 DEG C.The expansion process time is generally 5~10h.
Preferred scheme, the resin carbon source include at least one of phenolic resin, furane resins, Lauxite.
Preferred scheme, the mass ratio for expanding micro crystal graphite and resinae carbon source is 5~10:1.
Preferred scheme, the condition of the carbonization treatment are as follows: at a temperature of 800~1200 DEG C, 2~20h of soaking time.
Screening after micro crystal graphite ball milling is obtained the micro crystal graphite that partial size is 200~5000nm by technical solution of the present invention.
The present invention will expand micro crystal graphite using liquid phase method and be coated using resin carbon source.Detailed process are as follows: by resin carbon source
It is dissolved in solvent, expansion micro crystal graphite is added, be stirred by ultrasonic 2 hours and be uniformly mixed, obtain mixed liquor；It is dry, obtain hard carbon packet
Cover expansion microcrystalline graphite material presoma.
The present invention also provides the applications that hard carbon coats expansion microcrystalline graphite material, as sodium-ion battery cathode material
Material application.
The method that hard carbon cladding expansion microcrystalline graphite material of the invention prepares sodium-ion battery cathode: hard carbon is coated swollen
Swollen micro crystal graphite is mixed with conductive agent and binder, is coated in copper foil current collector by rubbing method, negative as sodium-ion battery
Pole.
Hard carbon cladding expansion micro crystal graphite prepared by the present invention prepares the method and property of sodium-ion battery as negative electrode material
It can detection method: the above-mentioned hard carbon cladding expansion micro crystal graphite of 80wt.% is weighed, 10wt.%Super P is added as conductive agent,
10wt.%PVDF is as binder, and ground sufficiently a small amount of NMP, which is added, is mixed to form uniform black paste slurry later, will
These slurries are coated in copper foil current collector as test electrode, are assembled into button cell using metallic sodium piece as comparison electrode,
It uses electrolyte system for 1M NaClO4/ EC:PC (1:1)+5%FEC, glass fibre is diaphragm, with CR2025 type stainless steel
Button cell is assembled into for battery case.
Compared with the prior art, the beneficial effects of the present invention are:
1) present invention utilizes micro crystal graphite and resin carbon source etc. for the first time, passes through ball-milling treatment, expanding treatment combination pyrocarbon
Change processing etc. prepares hard carbon cladding expansion microcrystalline graphite material, and this method is simple and reliable, reproducible, strong operability, environment
Friendly, low raw-material cost has apparent economic benefit, it is easy to accomplish industrialized production.
2) hard carbon of the invention cladding expansion microcrystalline graphite material is prepared using micro crystal graphite as raw material by expansion process
Micro crystal graphite is expanded out.In expansion procedure, the flocculent structure that micro crystal graphite extruding is formed is more advantageous to interelectric biography
It leads, improves the high rate performance of expansion micro crystal graphite；The cladding of hard carbon can alleviate expansion micro crystal graphite in charge and discharge simultaneously
Caused volume change in journey, while sodium can be stored up, improve the specific capacity and cyclical stability of material.These advantages make its spy
It is not suitable as anode material of lithium-ion battery use.
3) hard carbon-coated expansion microcrystalline graphite material of the invention is applied to sodium ion secondary battery field, tool for the first time
There are height ratio capacity, high coulombic efficiency, excellent high rate performance and high circulation stability.
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention；And the protection scope of the claims in the present invention
It is not limited by the example.
Embodiment 1
It takes 20g micro crystal graphite to be placed in ball grinder and carries out ball milling, ratio of grinding media to material 30:1, revolving speed 400rpm, Ball-milling Time
For 8h, resulting powder is sieved, collection cut size is the micro crystal graphite of 200~5000nm.By the concentrated sulfuric acid and micro crystal graphite
It is mixed evenly by liquid-solid ratio for 30:1L/kg；The mass volume ratio of the micro crystal graphite and hydrogen peroxide is added for 1:20g/mL
Enter hydrogen peroxide (technical grade), continues to stir 2h to after mixing evenly, be warming up to 60 DEG C at room temperature；Deionized water is added, is warming up to
100 DEG C are continued to stir 2h；Resulting mixed solution is subjected to vacuum filter, then filtrate is washed and is dried,
Up to inflatable micro crystal graphite；It gained be may expand into micro crystal graphite is put into graphite expansion furnace and carry out expansion 5h at 450 DEG C, obtain swollen
Swollen microcrystalline graphite material；1.5g phenolic resin is dissolved in 100ml ethyl alcohol, 10g is added and expands micro crystal graphite, ultrasonic agitation 2 is small
When be uniformly mixed, obtain mixed liquor, be evaporated to obtain hard carbon cladding expansion microcrystalline graphite material presoma in 80 DEG C of oil baths.By gained
To presoma be placed in tube furnace, in inert atmosphere, be further heat-treated at a temperature of 1100 DEG C, heating rate be 5 DEG C/
Min, soaking time 10h；After heat-treated products are washed repeatedly using deionized water and diluted acid, it is placed under the conditions of 70 DEG C of temperature,
It is dried in vacuo 12h, hard carbon cladding expansion microcrystalline graphite material can be obtained.The hard carbon cladding expansion microcrystalline graphite material shell
Hard carbon with a thickness of 8.6nm, specific surface area 28.35m2/g。
80wt.% hard carbon cladding expansion microcrystalline graphite material manufactured in the present embodiment is weighed, 10wt.%Super P is added
As conductive agent, 10wt.% sodium carboxymethylcellulose (CMC) is used as binder, ground that a small amount of deionization is sufficiently added later
Water is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode, with metal
Electrode assembling becomes button cell to sodium piece as a comparison, uses electrolyte system for 1M NaClO4/ EC:DEC (1:1)+5%
FEC, glass fibre are diaphragm, are assembled into button using CR2032 type stainless steel as battery case.In the current density of 100mA/g
Under, charge-discharge test is carried out to battery；The forthright again of battery is tested under the different current density such as 1000mA/g, 2000mA/g
Energy and cycle performance.Test result shows that the sodium-ion battery cathode of this example preparation has good chemical property:
Under the current density of 100mA/g, first circle coulombic efficiency is 38%, and first circle discharge capacity is 357mAh/g, after circulation 100 is enclosed,
Still it is able to maintain the specific capacity of 306mAh/g；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep 242mAh/ respectively
The specific capacity of g and 227mAh/g.1000 circle of circulation, capacity keep 197mAh/g under the power-discharging density of 2000mA/g.
Embodiment 2
It takes 20g micro crystal graphite to be placed in ball grinder and carries out ball milling, ratio of grinding media to material 40:1, revolving speed 300rpm, Ball-milling Time
For 8h, resulting powder is sieved, collection cut size is the micro crystal graphite of 200~5000nm.By the concentrated sulfuric acid and micro crystal graphite
It is mixed evenly by liquid-solid ratio for 30:1L/kg；The mass volume ratio of the micro crystal graphite and hydrogen peroxide is added for 1:20g/mL
Enter hydrogen peroxide (technical grade), continues to stir 2h to after mixing evenly, be warming up to 60 DEG C at room temperature；Deionized water is added, is warming up to
100 DEG C are continued to stir 2h；Resulting mixed solution is subjected to vacuum filter, then filtrate is washed and is dried,
It can must expand micro crystal graphite；Gained expansible graphite is put into graphite expansion furnace and carries out expansion 8h at 400 DEG C, must be expanded micro-
Spar ink material；1.5g phenolic resin is dissolved in 100ml ethyl alcohol, 10g is added and expands micro crystal graphite, is stirred by ultrasonic 2 hours and mixes
It closes uniformly, obtains mixed liquor, be evaporated to obtain hard carbon cladding expansion microcrystalline graphite material presoma in 80 DEG C of oil baths.It will be obtained
Presoma is placed in tube furnace, in inert atmosphere, is further heat-treated at a temperature of 950 DEG C, and heating rate is 5 DEG C/min, is protected
The warm time is 10h；It after heat-treated products are washed repeatedly using deionized water and diluted acid, is placed under the conditions of 70 DEG C of temperature, vacuum is dry
Hard carbon cladding expansion microcrystalline graphite material can be obtained in dry 12h.The hard carbon of the hard carbon cladding expansion microcrystalline graphite material shell
With a thickness of 5.9nm, specific surface area 36.23m2/g。
80wt.% hard carbon cladding expansion microcrystalline graphite material manufactured in the present embodiment is weighed, 10wt.%Super P is added
As conductive agent, 10wt.% sodium carboxymethylcellulose (CMC) is used as binder, ground that a small amount of deionization is sufficiently added later
Water is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode, with metal
Electrode assembling becomes button cell to sodium piece as a comparison, uses electrolyte system for 1M NaClO4/ EC:DEC (1:1)+5%
FEC, glass fibre are diaphragm, are assembled into button using CR2032 type stainless steel as battery case.In the current density of 100mA/g
Under, charge-discharge test is carried out to battery；The forthright again of battery is tested under the different current density such as 1000mA/g, 2000mA/g
Energy and cycle performance.Test result shows that the sodium-ion battery cathode of this example preparation has good chemical property:
Under the current density of 100mA/g, first circle coulombic efficiency is 38%, and first circle discharge capacity is 326mAh/g, after circulation 100 is enclosed,
Still it is able to maintain the specific capacity of 276mAh/g；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep 229mAh/ respectively
The specific capacity of g and 213mAh/g.1000 circle of circulation, capacity keep 174mAh/g under the power-discharging density of 2000mA/g.
Embodiment 3
It takes 20g micro crystal graphite to be placed in ball grinder and carries out ball milling, ratio of grinding media to material 20:1, revolving speed 600rpm, Ball-milling Time
For 8h, resulting powder is sieved, collection cut size is the micro crystal graphite of 200~5000nm.By the concentrated sulfuric acid and micro crystal graphite
It is mixed evenly by liquid-solid ratio for 30:1L/kg；The mass volume ratio of the micro crystal graphite and hydrogen peroxide is added for 1:20g/mL
Enter hydrogen peroxide (technical grade), continues to stir 2h to after mixing evenly, be warming up to 60 DEG C at room temperature；Deionized water is added, is warming up to
100 DEG C are continued to stir 2h；Resulting mixed solution is subjected to vacuum filter, then filtrate is washed and is dried,
It can must expand micro crystal graphite；It gained be may expand into micro crystal graphite is put into graphite expansion furnace and carry out expansion 8h at 500 DEG C, obtain swollen
Swollen microcrystalline graphite material；1g phenolic resin is dissolved in 100ml ethyl alcohol, 10g is added and expands micro crystal graphite, is stirred by ultrasonic 2 hours
It is uniformly mixed, obtains mixed liquor, be evaporated to obtain hard carbon cladding expansion microcrystalline graphite material presoma in 80 DEG C of oil baths.It will be acquired
Presoma be placed in tube furnace, in inert atmosphere, be further heat-treated at a temperature of 1100 DEG C, heating rate be 5 DEG C/min,
Soaking time is 10h；After heat-treated products are washed repeatedly using deionized water and diluted acid, it is placed under the conditions of 70 DEG C of temperature, vacuum
Hard carbon cladding expansion microcrystalline graphite material can be obtained in dry 12h.The hard carbon cladding expands the hard of microcrystalline graphite material shell
Carbon thickness is 4.3nm, specific surface area 16.58m2/g。
80wt.% hard carbon cladding expansion microcrystalline graphite material manufactured in the present embodiment is weighed, 10wt.%Super P is added
As conductive agent, 10wt.% sodium carboxymethylcellulose (CMC) is used as binder, ground that a small amount of deionization is sufficiently added later
Water is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode, with metal
Electrode assembling becomes button cell to sodium piece as a comparison, uses electrolyte system for 1M NaClO4/ EC:DEC (1:1)+5%
FEC, glass fibre are diaphragm, are assembled into button using CR2032 type stainless steel as battery case.In the current density of 100mA/g
Under, charge-discharge test is carried out to battery；The forthright again of battery is tested under the different current density such as 1000mA/g, 2000mA/g
Energy and cycle performance.Test result shows that the sodium-ion battery cathode of this example preparation has good chemical property:
Under the current density of 100mA/g, first circle coulombic efficiency is 43%, and first circle discharge capacity is 341mAh/g, after circulation 100 is enclosed,
Still it is able to maintain the specific capacity of 313mAh/g；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep 275mAh/ respectively
The specific capacity of g and 226mAh/g.1000 circle of circulation, capacity keep 187mAh/g under the power-discharging density of 2000mA/g.
Comparative example 1
It takes 20g micro crystal graphite to be placed in ball grinder and carries out ball milling, ratio of grinding media to material 30:1, revolving speed 400rpm, Ball-milling Time
For 8h, resulting powder is sieved, collection cut size is the micro crystal graphite of 200~5000nm.By the concentrated sulfuric acid and micro crystal graphite
It is mixed evenly by liquid-solid ratio for 30:1L/kg；The mass volume ratio of the micro crystal graphite and hydrogen peroxide is added for 1:20g/mL
Enter hydrogen peroxide (technical grade), continues to stir 2h to after mixing evenly, be warming up to 60 DEG C at room temperature；Deionized water is added, is warming up to
100 DEG C are continued to stir 2h；Resulting mixed solution is subjected to vacuum filter, then filtrate is washed and is dried,
It can must expand micro crystal graphite；It gained be may expand into micro crystal graphite is put into graphite expansion furnace and carry out expansion 5h at 450 DEG C, obtain swollen
Swollen microcrystalline graphite material, specific surface area 10.67m2/g。。
80wt.% expansion microcrystalline graphite material manufactured in the present embodiment is weighed, 10wt.%Super P is added as conductive
Agent, 10wt.% sodium carboxymethylcellulose (CMC) is used as binder, ground that a small amount of deionized water mixing shape is sufficiently added later
At uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode, using metallic sodium piece as
Comparison electrode is assembled into button cell, uses electrolyte system for 1M NaClO4/ EC:DEC (1:1)+5%FEC, glass
Fiber is diaphragm, is assembled into button using CR2032 type stainless steel as battery case.Under the current density of 100mA/g, to electricity
Pond carries out charge-discharge test；The high rate performance of battery is tested under the different current density such as 1000mA/g, 2000mA/g and is followed
Ring performance.Test result shows that the sodium-ion battery cathode of this example preparation has good chemical property: 100mA/g's
Under current density, first circle coulombic efficiency is 43%, and first circle discharge capacity is that 246mAh/g is still able to maintain after circulation 100 is enclosed
The specific capacity of 178mAh/g；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep respectively 165mAh/g and
The specific capacity of 141mAh/g.1000 circle of circulation, capacity keep 118mAh/g under the power-discharging density of 2000mA/g.
Comparative example 2
It takes 20g micro crystal graphite to be placed in ball grinder and carries out ball milling, ratio of grinding media to material 30:1, revolving speed 400rpm, Ball-milling Time
For 8h, resulting powder is sieved, collection cut size is the micro crystal graphite of 200~5000nm.1.5g phenolic resin is dissolved in
In 100ml ethyl alcohol, 10g micro crystal graphite is added, is stirred by ultrasonic 2 hours and is uniformly mixed, obtain mixed liquor, be evaporated in 80 DEG C of oil baths
Microcrystalline graphite material presoma is coated to hard carbon.Obtained presoma is placed in tube furnace, in inert atmosphere, at 1100 DEG C
At a temperature of be further heat-treated, heating rate be 5 DEG C/min, soaking time 10h；Heat-treated products using deionized water with it is dilute
It after acid washs repeatedly, is placed under the conditions of 70 DEG C of temperature, is dried in vacuo 12h, hard carbon cladding microcrystalline graphite material can be obtained.
80wt.% hard carbon cladding microcrystalline graphite material manufactured in the present embodiment is weighed, 10wt.%Super P conduct is added
Conductive agent, 10wt.% sodium carboxymethylcellulose (CMC) are used as binder, it is ground sufficiently after that a small amount of deionized water is added is mixed
Conjunction forms uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode, with metallic sodium piece
Electrode assembling becomes button cell as a comparison, uses electrolyte system for 1M NaClO4/ EC:DEC (1:1)+5%FEC,
Glass fibre is diaphragm, is assembled into button using CR2032 type stainless steel as battery case.Under the current density of 100mA/g,
Charge-discharge test is carried out to battery；The high rate performance of battery is tested under the different current density such as 1000mA/g, 2000mA/g
And cycle performance.Test result shows that the sodium-ion battery cathode of this example preparation has good chemical property: in 100mA/
Under the current density of g, first circle coulombic efficiency is 28%, and first circle discharge capacity is that 157mAh/g remains to protect after circulation 100 is enclosed
Hold the specific capacity of 116mAh/g；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep respectively 104mAh/g and
The specific capacity of 87mAh/g.1000 circle of circulation, capacity keep 64mAh/g under the power-discharging density of 2000mA/g.
Claims (9)
1. a kind of hard carbon cladding expansion microcrystalline graphite material, it is characterised in that: coat expansion micro crystal graphite by hard carbon layer and constitute.
2. a kind of hard carbon cladding expansion microcrystalline graphite material according to claim 1, it is characterised in that:
The hard carbon layer with a thickness of 5~50nm, the partial size of hard carbon cladding expansion microcrystalline graphite material is 200~5000nm；Firmly
The specific surface area that carbon coating expands microcrystalline graphite material is 2~100m2/g。
3. a kind of preparation method of hard carbon cladding expansion microcrystalline graphite material of any of claims 1 or 2, it is characterised in that: packet
Include following steps:
1) by micro crystal graphite ball-milling treatment, micro crystal graphite powder is obtained；
2) by micro crystal graphite powder after chemical graft is handled, expansion process is carried out, obtains expansion micro crystal graphite；
3) after the expansion micro crystal graphite is using resin carbon source cladding, carbonization treatment is carried out to get hard carbon and coats expansion microlite
Black composite material.
4. a kind of preparation method of hard carbon cladding expansion microcrystalline graphite material according to claim 3, it is characterised in that: institute
State the condition of ball milling are as follows: Ball-milling Time is 4~8 hours, and revolving speed is 300~600r/min, and ball material mass ratio is 20~40:1.
5. a kind of preparation method of hard carbon cladding expansion microcrystalline graphite material according to claim 3, it is characterised in that: institute
Stating chemical graft processing uses the concentrated sulfuric acid for intercalator, and hydrogen peroxide is oxidant.
6. a kind of preparation method of hard carbon cladding expansion microcrystalline graphite material according to claim 3, it is characterised in that: institute
The temperature for stating expansion process is 400~500 DEG C.
7. a kind of preparation method of hard carbon cladding expansion microcrystalline graphite material according to claim 3, it is characterised in that: institute
Stating resin carbon source includes at least one of phenolic resin, furane resins, Lauxite；
The mass ratio for expanding micro crystal graphite and resinae carbon source is 5~10:1.
8. the preparation method of hard carbon cladding expansion microcrystalline graphite material according to claim 3, it is characterised in that: the carbon
Change the condition of processing are as follows: at a temperature of 800~1200 DEG C, 2~20h of soaking time.
9. the application of hard carbon cladding expansion microcrystalline graphite material of any of claims 1 or 2, it is characterised in that: as sodium ion
Cell negative electrode material application.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111613785A (en) * | 2020-05-28 | 2020-09-01 | 贝特瑞新材料集团股份有限公司 | Composite coated negative electrode material, preparation method thereof and lithium ion battery |
| CN112670463A (en) * | 2020-04-16 | 2021-04-16 | 宁波杉杉新材料科技有限公司 | Graphite negative electrode material and preparation method and application thereof |
| CN114195123A (en) * | 2021-12-30 | 2022-03-18 | 上海杉杉新材料有限公司 | Modified hard carbon material, preparation method and application thereof |
| CN114361410A (en) * | 2021-12-13 | 2022-04-15 | 苏州蔚利昆新能源科技有限公司 | Fast charging lithium battery |
| CN116216708A (en) * | 2023-02-14 | 2023-06-06 | 广东邦普循环科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN116914125A (en) * | 2023-09-12 | 2023-10-20 | 深圳市贝特瑞新能源技术研究院有限公司 | Micro-expansion modified microcrystalline graphite negative electrode material and preparation method and application thereof |
| CN118099400A (en) * | 2024-04-23 | 2024-05-28 | 上海兆钠新能源科技有限公司 | Expanded graphite material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078090A (en) * | 2013-03-01 | 2013-05-01 | 湖州创亚动力电池材料有限公司 | Lithium ion power battery composite cathode material and its preparation method |
| CN103265020A (en) * | 2013-05-27 | 2013-08-28 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene quantum dot powder on large scale |
| CN104377346A (en) * | 2014-11-04 | 2015-02-25 | 辽宁工程技术大学 | Method for preparing modified graphite negative electrode material of sodium ion battery |
| CN106252627A (en) * | 2016-08-30 | 2016-12-21 | 浙江和也健康科技有限公司 | A kind of preparation method of cathode material of lithium-ion power battery |
| CN108155022A (en) * | 2017-12-23 | 2018-06-12 | 林荣铨 | Use the preparation method of the lithium-ion capacitor of carbon nanotube/Lauxite carbon coating spherical shape microcrystalline graphite material |
-
2018
- 2018-12-05 CN CN201811476709.3A patent/CN109616639B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078090A (en) * | 2013-03-01 | 2013-05-01 | 湖州创亚动力电池材料有限公司 | Lithium ion power battery composite cathode material and its preparation method |
| CN103265020A (en) * | 2013-05-27 | 2013-08-28 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene quantum dot powder on large scale |
| CN104377346A (en) * | 2014-11-04 | 2015-02-25 | 辽宁工程技术大学 | Method for preparing modified graphite negative electrode material of sodium ion battery |
| CN106252627A (en) * | 2016-08-30 | 2016-12-21 | 浙江和也健康科技有限公司 | A kind of preparation method of cathode material of lithium-ion power battery |
| CN108155022A (en) * | 2017-12-23 | 2018-06-12 | 林荣铨 | Use the preparation method of the lithium-ion capacitor of carbon nanotube/Lauxite carbon coating spherical shape microcrystalline graphite material |
Non-Patent Citations (2)
| Title |
|---|
| YANG WEN等: "Expanded graphite as superior anode for sodium-ion batteries", 《NATURE COMMUNICATIONS》 * |
| YUXIANG CHEN等: "Tailoring graphitic nanostructures in hard carbons as anode materials achieving efficient and ultrafast sodium storage", 《J. MATER. SCI.》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112670463A (en) * | 2020-04-16 | 2021-04-16 | 宁波杉杉新材料科技有限公司 | Graphite negative electrode material and preparation method and application thereof |
| CN111613785A (en) * | 2020-05-28 | 2020-09-01 | 贝特瑞新材料集团股份有限公司 | Composite coated negative electrode material, preparation method thereof and lithium ion battery |
| CN114361410A (en) * | 2021-12-13 | 2022-04-15 | 苏州蔚利昆新能源科技有限公司 | Fast charging lithium battery |
| CN114361410B (en) * | 2021-12-13 | 2024-04-16 | 苏州蔚利昆新能源科技有限公司 | Quick-charging lithium battery |
| CN114195123A (en) * | 2021-12-30 | 2022-03-18 | 上海杉杉新材料有限公司 | Modified hard carbon material, preparation method and application thereof |
| CN116216708A (en) * | 2023-02-14 | 2023-06-06 | 广东邦普循环科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN116216708B (en) * | 2023-02-14 | 2024-04-09 | 广东邦普循环科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN116914125A (en) * | 2023-09-12 | 2023-10-20 | 深圳市贝特瑞新能源技术研究院有限公司 | Micro-expansion modified microcrystalline graphite negative electrode material and preparation method and application thereof |
| CN116914125B (en) * | 2023-09-12 | 2023-12-05 | 深圳市贝特瑞新能源技术研究院有限公司 | Micro-expansion modified microcrystalline graphite negative electrode material and preparation method and application thereof |
| CN118099400A (en) * | 2024-04-23 | 2024-05-28 | 上海兆钠新能源科技有限公司 | Expanded graphite material and preparation method and application thereof |
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