CN103199225B - Silicon-carbon cathode material, its preparation method and a kind of lithium ion battery - Google Patents
Silicon-carbon cathode material, its preparation method and a kind of lithium ion battery Download PDFInfo
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- CN103199225B CN103199225B CN201310143242.1A CN201310143242A CN103199225B CN 103199225 B CN103199225 B CN 103199225B CN 201310143242 A CN201310143242 A CN 201310143242A CN 103199225 B CN103199225 B CN 103199225B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Organo-silicon compound are mixed, react and obtain silicon pyrolytic material by the present invention with reducing agent first；Then by itself and graphite ball milling mixing, silicon pyrolysis carbon material is obtained；Obtained silicon pyrolysis carbon material is performed etching in acid solution again, is then mixed with the salting liquid of metal ion, deposited metal and its oxide, obtains silicon-carbon cathode material.The present invention use organosilicon cheap and easy to get as raw material, in Si-C composite material the Surface coating preferable metal level of electric conductivity and the metal oxide layer of preparation, formation conductive network, improves the electric conductivity of material；Meanwhile the metal and its oxide coated can effectively reduce volumetric expansion and the mechanical stress in lithium ion charge and discharge process, make the composite of preparation there is longer cycle life.
Description
Technical field
The present invention relates to electrode material technical field, more particularly to a kind of silicon-carbon cathode material, its preparation method and one kind
Lithium ion battery.
Background technology
Lithium ion battery is and wide due to having the advantages that operating voltage is high, bigger than energy, self discharge is small and low in the pollution of the environment
It is general to be applied to civil and military field.Wherein negative material has important to the security, cycle life and energy density of lithium battery
Influence, be the key factor of lithium ion battery technology progress.
At present, the widely used negative material of lithium ion battery is graphite material, its have it is cheap and easily-available, in light weight and
The superiority such as thermal coefficient of expansion is small, but its theoretical lithium storage content is only 372mAh/g, with the fast development of science and technology, can not
Meets the needs of lithium ion battery is as energy-storage battery.In order to improve the capacitance of lithium ion battery, meet novel device to height
The demand of specific capacity battery, it is necessary to seek the electrode material with higher theoretical lithium storage content, or carried out to graphite material
It is modified, higher theoretical lithium storage content is made it have, because silicon has 4200mAh/g theoretical capacity value, therefore silicon-carbon is compound
Negative material becomes study hotspot.
Prior art discloses silicon nanoparticle is deposited in graphite by chemical deposition, silicon-carbon composite wood is prepared
Material, then lithium insertion graphite layers are formed to the technology of lithium ion battery negative material again, but this technology, lithium ion is embedding
Volume easily occurs seriously to expand during entering, and causes material that efflorescence, electrode material meeting portion can occur after multiple discharge and recharge
Divide and come off, substantially reduce battery life；Meanwhile the electric conductivity of silicon is also be not as good as carbon material so that the electrode material of preparation
Electric conductivity is affected.
The content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of silicon-carbon cathode material, its preparation method and
A kind of lithium ion battery, the silicon-carbon cathode material of preparation not only have good electric conductivity, also have longer cycle life.
The invention provides a kind of preparation method of silicon-carbon cathode material, including：
A）Organo-silicon compound are mixed with reducing agent, reacts and obtains silicon-pyrolytic material；
B）By step A）Obtained silicon-pyrolytic material and graphite ball milling mixing, obtain silicon-pyrolysis carbon material；
C）By step B）Obtained silicon-pyrolysis carbon material performs etching in acid solution, then with the salt of metal ion
Solution mixes, and deposited metal and its oxide, obtains silicon-carbon cathode material.
Preferably, the metal ion is selected from Fe2+、Fe3+、Sn2+And Ti4+In any one or a few.
Preferably, any one or a few in nickel-base catalyst, sodium borohydride and lithium aluminium hydride reduction of the reducing agent.
Preferably, any one or a few in silane coupler, silicone oil and silicones of the organo-silicon compound.
Preferably, the step A）In, the temperature of the reaction is 600 DEG C~900 DEG C, time of the reaction for 2h~
4h。
Preferably, the acid solution includes any one in nitric acid, hydrochloric acid or sulfuric acid and hydrofluoric acid and water.
Preferably, also include after the step of deposited metal and its oxide：After deposited metal and its oxide
Material is heated, and obtains silicon-carbon cathode material；The temperature of the heating is 300 DEG C~1200 DEG C.
Present invention also offers a kind of silicon-carbon cathode material, for Si-C composite material surface clad and its oxide
Into.
Preferably, in the metal and its oxide, the metal is any one or a few in Fe, Sn and Ti.
Present invention also offers a kind of lithium ion battery, its negative pole is that the silicon-carbon prepared using method provided by the invention is born
Pole material.
Organo-silicon compound are mixed, react and obtain silicon-pyrolytic material by the present invention with reducing agent first；Then by itself and stone
Black ball milling mixing, obtain silicon-pyrolysis carbon material；Obtained silicon-pyrolysis carbon material is performed etching in acid solution again, Ran Houyu
The salting liquid mixing of metal ion, deposited metal and its oxide, obtain silicon-carbon cathode material.The present invention is using cheap and easy to get
Organosilicon be raw material, in Si-C composite material the Surface coating preferable metal level of electric conductivity and the metal oxide of preparation
Layer, conductive network is formed, improve the electric conductivity of material；Meanwhile the metal and oxide skin(coating) coated can be reduced effectively
Volumetric expansion and mechanical stress in lithium ion charge and discharge process, make the composite of preparation have longer cycle life.
The metal-modified silicon-carbon cathode material prepared using the present invention prepares battery, and carries out performance detection, the results showed that,
The battery initial energy density of preparation can reach 623mAh/g, and after 50 circulations, capability retention is more than 92%；And its volume
With weight compared with battery prepared by graphite material, about 12% and 11% can be separately optimized.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram of silicon-carbon cathode material prepared by the embodiment of the present invention 1；
Fig. 2 is the discharge curve of battery prepared by the embodiment of the present invention 4；
Fig. 3 is the cyclic curve figure of battery prepared by the embodiment of the present invention 4.
Embodiment
The invention provides a kind of preparation method of silicon-carbon cathode material, including：
A）Organo-silicon compound are mixed with reducing agent, reacts and obtains silicon-pyrolytic material；
B）By step A）Obtained silicon-pyrolytic material and graphite ball milling mixing, obtain silicon-pyrolysis carbon material；
C）By step B）Obtained silicon-pyrolysis carbon material performs etching in acid solution, then with the salt of metal ion
Solution mixes, and deposited metal and its oxide, obtains silicon-carbon cathode material.
Organo-silicon compound are mixed, react and obtain silicon-pyrolytic material by the present invention with reducing agent first；Then by itself and stone
Black ball milling mixing, obtain silicon-pyrolysis carbon material；Obtained silicon-pyrolysis carbon material is performed etching in acid solution again, Ran Houyu
The salting liquid mixing of metal ion, deposited metal and its oxide, obtain silicon-carbon cathode material.The present invention is using cheap and easy to get
Organosilicon be raw material, in Si-C composite material the Surface coating preferable metal level of electric conductivity and the metal oxide of preparation
Layer, conductive network is formed, improve the electric conductivity of material；Meanwhile the metal and its oxide skin(coating) coated can effectively drop
Volumetric expansion and mechanical stress in low lithium ion charge and discharge process, make the composite of preparation have longer cycle life.
Organo-silicon compound are mixed, react and obtain silicon-pyrolytic material by the present invention with reducing agent first.It is described siliconated
Compound preferably uses any one or a few in silane coupler, silicone oil and silicones；More preferably use silane coupler；Institute
It is preferably any one or a few in nickel-base catalyst, sodium borohydride and lithium aluminium hydride reduction to state reducing agent；It is more preferably Ni-based to urge
Agent.The present invention, without particular/special requirement, can be general commercially available to the source of the organo-silicon compound and reducing agent.The present invention
In, the temperature of the reaction is preferably 600 DEG C~900 DEG C, more preferably 750 DEG C~850 DEG C；The time of the reaction be 2h~
4h, more preferably 2.5h~3.5h.The reaction is preferably carried out under the protection of inert gas, and the inert gas is preferably nitrogen
Gas.
After obtaining silicon-pyrolytic material, by itself and graphite ball milling mixing, silicon-pyrolysis carbon material is obtained；The silicon-pyrolysis material
The mass ratio of material and graphite is preferably 1：（1~3）, more preferably 1：（1.5~2.5）；Source of the invention to the graphite is simultaneously
Can be general commercially available without particular/special requirement.
Then, obtained silicon-pyrolysis carbon material is performed etching in acid solution, the acid solution preferably include nitric acid,
Any one in hydrochloric acid or sulfuric acid and hydrofluoric acid and water；The mass ratio of the nitric acid, hydrochloric acid or sulfuric acid and hydrofluoric acid, water is preferred
For 1：（2~4）：（5~7）；The present invention does not have particular/special requirement to the method for the etching, can be that those skilled in the art are ripe
The lithographic method known, currently preferred, the method that stirring or ultrasonic vibration etching can be used；The time of the etching is preferred
For 2min~30min；After being performed etching to the silicon-pyrolysis carbon material, it is preferred that it is cleaned using distilled water, this
Invention does not have particular/special requirement to the method for the cleaning, can be in general cleaning method, it is preferred that surpassed using deionized water
The method that cleaning is swung in acoustic shock；Material after cleaning is filtered into the silicon after being surface-treated-pyrolysis carbon material.
Silicon after obtained surface treatment-pyrolysis carbon material is mixed with the salting liquid of metal ion, deposited metal and
Its oxide, you can obtain silicon-carbon cathode material.In the salting liquid of the metal ion, the metal ion is preferably Fe2+、
Fe3+、Sn2+And Ti4+In any one or a few；The present invention is in the salting liquid, the species of anion has no special limit
It is fixed, can be sulfate radical, nitrate anion, chlorion, acetate；The salting liquid of the metal ion is preferably ferric sulfate, sulfuric acid
Ferrous iron, STANNOUS SULPHATE CRYSTALLINE, titanium sulfate, ferrous nitrate, ferric nitrate, nitric acid tin, four Titanium Nitrates, frerrous chloride, iron chloride, stannic chloride, four
Any one or a few in titanium chloride, ferrous acetate, ferric acetate, tin acetate and acetic acid titanium, more preferably ferrous sulfate, nitric acid
Any one or a few in iron, STANNOUS SULPHATE CRYSTALLINE, titanium sulfate and titanium tetrachloride；The concentration of the salting liquid of the metal ion is preferred
For 1mol/L~5mol/L；It contains Fe2+、Fe3+、Sn2+And Ti4+Mol ratio be preferably（0~0.8）：（0~0.8）：（0~1）：
（0~1）, more preferably（0~0.4）：（0~0.4）：（0~1）：（0~1）, and Fe2+、Fe3+、Sn2+And Ti4+Can not be simultaneously
For 0；In the deposited metal and its oxide, the metal is preferably any one or a few in Fe, Sn and Ti, preferably
, the metal and its oxide can be selected from Fe and Fe2O3, either selected from Sn and SnO or selected from Ti and TiO2, Huo Zhexuan
From Fe, Fe2O3, Sn and SnO；Or selected from Fe, Fe2O3, Ti and TiO2；Or selected from Sn, SnO, Ti and TiO2；Or it is selected from
Fe、Fe2O3, Sn, SnO, Ti and TiO2；Gross mass and the tin of the deposition iron and its oxi and its gross mass of oxide and
The ratio of the gross mass of titanium and its oxide is preferably（0~0.8）：（0~1）：（0~1）, and iron and its oxi, tin and its
Oxide and titanium and its oxide can not be 0 simultaneously.
The present invention can form conductive network in silicon-carbon cathode material surface deposited metal and metal oxide layer, improve material
The electric conductivity of material；Also, the metal and metal oxide layer can greatly improve the lithium storage content of negative material, make material
Material has higher capacitance；Meanwhile the metal and its oxide skin(coating) coated can effectively reduce lithium ion charge and discharge process
In volumetric expansion and mechanical stress, make the composite of preparation there is longer cycle life.
After deposited metal and its oxide, it is preferred that also include adding the material after deposited metal and its oxide
Heat, obtain silicon-carbon cathode material；The temperature of the heating is preferably 300 DEG C~1200 DEG C, more preferably 500 DEG C~1000 DEG C；
The time of the heating is preferably 1h~3h；More preferably 1.5h~2.5h.Preferably, the heating is entered in reducibility gas
OK, the present invention to the reducibility gas and is not particularly limited, and can be reducibility gas well known to those skilled in the art, excellent
Elect the mixed gas or CO gas of hydrogen and nitrogen as；The volume ratio of the hydrogen and nitrogen is preferably（2~3）：
1.Material after deposited metal and its oxide is heated, is advantageous to increase the knot of metal ion and silicon-pyrolysis carbon material
Conjunction ability, improve the cycle performance of material.
Present invention also offers a kind of silicon-carbon cathode material, for Si-C composite material surface clad and its oxide
Into.In the metal and its oxide, the metal is preferably any one or a few of Fe, Sn and Ti；Preferably, the gold
Category and its oxide can be selected from Fe and Fe2O3, Sn and SnO, Ti and TiO2In any one or a few, and Fe and Fe2O3Must
Must exist simultaneously, Sn and SnO must exist simultaneously, Ti and TiO2Must exist simultaneously；The gross mass of the iron and its oxi
Ratio with the gross mass and titanium of tin and its oxide and its gross mass of oxide is preferably（0~0.8）：（0~1）：（0~
1）, and iron and its oxi, tin and its oxide and titanium and its oxide can not be 0 simultaneously.
Shape measure is carried out to silicon-carbon cathode material provided by the invention using SEM, the results showed that, this
The silicon-carbon cathode material that invention provides is micron-scale, and is lamella packed structures；Pore-size distribution test result is shown, of the invention
A diameter of 5~10 microns of the silicon-carbon cathode material of offer, and there is larger specific surface area.
Present invention also offers a kind of battery, its negative pole is the silicon-carbon cathode material prepared according to method provided by the invention
Or use silicon-carbon cathode material provided by the invention.The present invention has no particular/special requirement, Ke Yiwei to the positive electrode of the battery
Cell positive material well known to those skilled in the art, the present invention are preferably LiMn2O4 or LiFePO4.
Specifically, silicon-carbon cathode material is mixed with conductive agent and binding agent, it is applied in copper foil current collector and negative electricity is made
Core；Positive electrode is mixed with conductive agent and binding agent simultaneously, is applied in aluminum foil current collector and positive pole battery core is made；The present invention is to institute
State conductive agent and binding agent has no particular/special requirement, can be the conductive agent well known to those skilled in the art that can be used for preparing battery
And binding agent, currently preferred, the conductive agent is acetylene black, carbon black or graphite, and the binding agent is Kynoar, gathered
Vinyl alcohol, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose or polyurethane；The negative material or positive electrode and conductive agent, bonding
The weight ratio of agent is preferably（80~90）：（5~10）；（5~10）, and each component content summation is 100；Then by the negative of preparation
Pole battery core and positive pole battery core are sealed using plastic pressuring process, you can lithium ion battery is made.The electric capacity of the lithium ion battery
Measure as 10Ah~200Ah.
Performance detection is carried out to the battery of preparation, the results showed that, its initial energy density can reach 623mAh/g, follow for 50 times
After ring, capability retention is more than 92%, and its volume and weight has been separately optimized about 12% and 10.7%.
The present invention uses organosilicon cheap and easy to get as raw material, in the Si-C composite material Surface coating electric conductivity of preparation
Preferable metal level and metal oxide layer, form conductive network, improve the electric conductivity of material；Also, the metal and
Metal oxide layer can greatly improve the lithium storage content of negative material, material is had higher capacitance；Meanwhile wrapped
The metal and its oxide skin(coating) covered can effectively reduce volumetric expansion and mechanical stress in lithium ion charge and discharge process, make preparation
Composite there is longer cycle life.Also, the material prepared is nanoscale, can reduce material volume in conducting process
Absolute change value, shorten the diffusion path of lithium ion, so as to improve the electronic conductivity energy of prepared silicon-carbon cathode material,
Therefore, silicon-carbon cathode material provided by the invention, not only with good electric conductivity, also there is longer cycle life.
In order to further illustrate the present invention, with reference to embodiment to silicon-carbon cathode material provided by the invention and its preparation
Method is described in detail.
Embodiment 1
Silane coupler 1g is mixed with 0.05g nickel-base catalysts, after stirring, under the protection of nitrogen, in 800 DEG C
Under conditions of heating response 3h, obtain silicon-pyrolytic material；Obtained silicon-pyrolytic material 1g and graphite 1.5g ball milling mixings is equal
After even, silicon-pyrolysis carbon material is obtained；Obtained silicon-pyrolysis carbon material is scattered in acid solution and etches 4min, the acid solution
It is 10 for mass ratio:30:The mixed solution of 60 65wt% hydrofluoric acid, 50wt% nitric acid and water, will after ultrasonic vibration etching 4min
Material is cleaned with distilled water ultrasonic vibration and removes surface acid solution, is filtrated to get solid, obtained solid is dispersed in into concentration
In 2mol/L copperas solution, make Fe and Fe2O3The silicon-pyrolysis carbon material surface is deposited on, is then 3 in volume ratio:
In 1 hydrogen and the mixed gas of nitrogen, 1h is heated under 400 DEG C of temperature conditionss, obtains silicon-carbon cathode material.
Shape measure is carried out to the silicon-carbon cathode material of preparation by SEM, experimental result is shown in Fig. 1, Fig. 1
It is the scanning electron microscope diagram of silicon-carbon cathode material prepared by embodiment 1.As shown in Figure 1, silicon-carbon cathode provided by the invention
Material is that micron-sized lamella accumulates material.
Pore-size distribution test is carried out to the silicon-carbon cathode material of preparation, the results showed that, silicon-carbon cathode material prepared by the present invention
A diameter of 9.486 μm of material, its specific surface area is 23.947m2/ g, density 0.54g/cm3。
Its component is detected, the results showed that, silicon-carbon cathode material prepared by the present invention includes：75.7wt% carbon,
21.2wt% silicon and 2.8wt% iron and 0.3wt% di-iron trioxides.
Embodiment 2
Silane coupler 1g is mixed with 0.05g nickel-base catalysts, after stirring, under the protection of nitrogen, in 800 DEG C
Under conditions of heating response 3h, obtain silicon-pyrolytic material；Obtained silicon-pyrolytic material 1g and graphite 1.5g ball milling mixings is equal
After even, silicon-pyrolysis carbon material is obtained；Obtained silicon-pyrolysis carbon material is scattered in acid solution, ultrasonic vibration etching 10min,
The acid solution is that mass ratio is 10:30:The mixed solution of 60 hydrofluoric acid, nitric acid and water, after etching 10min, material is used
After the cleaning of distilled water ultrasonic vibration, solid is filtrated to get, obtained solid is dispersed in concentration 2mol/L sulfuric acid solution of tin,
Sn and SnO is deposited on the silicon-pyrolysis carbon material surface, be then 2 in volume ratio:1 hydrogen and the mixed gas of nitrogen
In, 1h is heated under 800 DEG C of temperature conditionss, obtains silicon-carbon cathode material.
Shape measure is carried out to the silicon-carbon cathode material of preparation by SEM, test result indicates that, this hair
The silicon-carbon cathode material of bright offer is that micron-sized lamella accumulates material.
Pore-size distribution test is carried out to the silicon-carbon cathode material of preparation, the results showed that, silicon-carbon cathode material prepared by the present invention
A diameter of 5.452 μm of material, its specific surface area is 17.655m2/ g, density 0.46g/cm3。
Its component is detected, the results showed that, silicon-carbon cathode material prepared by the present invention includes：77.6wt% carbon,
19.8wt% silicon and 2.0wt% tin and 0.6wt% tin oxide.
Embodiment 3
Silane coupler 1g is mixed with 0.05g nickel-base catalysts, after stirring, under the protection of nitrogen, in 800 DEG C
Under conditions of heating response 3h, obtain silicon-pyrolytic material；Obtained silicon-pyrolytic material 1g and graphite 1.5g ball milling mixings is equal
After even, silicon-pyrolysis carbon material is obtained；Obtained silicon-pyrolysis carbon material is scattered in acid solution, ultrasonic vibration etching 2min,
The acid solution is that mass ratio is 10:30:The mixed solution of 60 hydrofluoric acid, nitric acid and water, after etching 2min, by material steaming
After the cleaning of distilled water ultrasonic vibration, solid is filtrated to get, obtained solid is dispersed in concentration 2mol/L titanium sulfate solution, made
Ti and TiO2The silicon-pyrolysis carbon material surface is deposited on, is then 2 in volume ratio:1 hydrogen and the mixed gas of nitrogen
In, 1h is heated under 1000 DEG C of temperature conditionss, obtains silicon-carbon cathode material.
Shape measure is carried out to the silicon-carbon cathode material of preparation by SEM, test result indicates that, this hair
The silicon-carbon cathode material of bright offer is that micron-sized lamella accumulates material.
Pore-size distribution test is carried out to the silicon-carbon cathode material of preparation, the results showed that, silicon-carbon cathode material prepared by the present invention
A diameter of 6.722 μm of material, its specific surface area is 15.782m2/ g, density 0.54g/cm3。
Its component is detected, the results showed that, silicon-carbon cathode material prepared by the present invention includes：77.5wt% carbon,
20.1wt% silicon and 2.0wt% titanium and 0.4wt% titanium dioxide.
Embodiment 4
Silicon-carbon cathode material prepared by embodiment 1 is with acetylene black conductor and Kynoar binding agent by 90：5：5
Mass ratio is mixed, and is applied in copper foil current collector and battery core is made, and positive pole is used LiMn2O4 and acetylene black conductor and polyvinylidene fluoride
Alkene binding agent presses 90：5：Manufactured battery core in aluminum foil current collector is applied to after 5 mass ratio mixing, it is carried out using plastic pressuring process
Sealing, the rectangular lithium ion battery that capacity is 50Ah is made.Electrochemical property test, test are carried out to the lithium ion battery of preparation
As a result Fig. 2 and Fig. 3 are seen.Fig. 2 is the discharge curve of battery prepared by the embodiment of the present invention 4；Fig. 3 is that the embodiment of the present invention 4 is made
The cyclic curve figure of standby battery；From Fig. 2 and Fig. 3, the battery prepared using silicon-carbon cathode material provided by the invention, its
Initial energy density can reach 623mAh/g, and after 50 circulations, capability retention is more than 92%.
The battery outward appearance of preparation is detected, the results are shown in Table 1, table 1 is prepared by the embodiment of the present invention 4 and comparative example 1
The volume of battery, weight contrast；As shown in Table 1, the battery prepared using silicon-carbon cathode material provided by the invention, is born with graphite
Pole battery is compared, and its volume can reduce 12%, and weight can mitigate 10.7%.
Comparative example 1
Native graphite 10g is mixed with phenolic resin 2g, 150 DEG C are sintered, and system then is cooled into room temperature（25
℃）Afterwards, product is crushed using spherical grinder, then the product after crushing is sieved, obtains coating modification
Graphite cathode material.
The graphite cathode material of preparation is used to press itself and acetylene black conductor and Kynoar binding agent for negative pole
90：5：5 mass ratio mixing, is applied in copper foil current collector and battery core is made, positive pole use LiMn2O4 and acetylene black conductor and
Kynoar binding agent presses 90：5：Manufactured battery core in aluminum foil current collector is applied to after 5 mass ratio mixing, uses plastic pressuring process
It is sealed, the rectangular lithium ion battery that capacity is 50Ah is made.The battery outward appearance of preparation is detected, the results are shown in Table
1, table 1 is the volume of the battery of the embodiment of the present invention 4 and the preparation of comparative example 1, weight contrast.
The volume of battery prepared by the embodiment of the present invention 4 of table 1 and comparative example 1, weight contrast
| Test event | Embodiment 4 | Comparative example 1 |
| Volume（mm） | 132×170×325 | 132×193×325 |
| Volume reduces | 12% | - |
| Weight（kg） | 12.5 | 14 |
| Weight saving | 10.7% | - |
Comparative example 2
Native graphite 10g is mixed with phenolic resin 2g, 150 DEG C are sintered, and then add silane coupler 3g ball millings
Mixing, Si-C composite material is made.
The Si-C composite material of preparation is used to press itself and acetylene black conductor and Kynoar binding agent for negative pole
90：5：5 mass ratio mixing, is applied in copper foil current collector and battery core is made, positive pole use LiMn2O4 and acetylene black conductor and
Kynoar binding agent presses 90：5：Manufactured battery core in aluminum foil current collector is applied to after 5 mass ratio mixing, uses plastic pressuring process
It is sealed, the rectangular lithium ion battery that capacity is 50Ah is made.Electrochemical property test, knot are carried out to the battery of preparation
Fruit shows that its initial energy density is 732mAh/g；After 50 circulations, capability retention 67%.
Embodiment 5
Silicon-carbon cathode material prepared by embodiment 2 is with acetylene black conductor and Kynoar binding agent by 90：5：5
Mass ratio mixes, and is applied in copper foil current collector and battery core is made, and positive pole uses LiFePO4 and acetylene black conductor and gathers inclined fluorine
Ethene binding agent presses 90：5：Manufactured battery core in aluminum foil current collector is applied to after 5 mass ratio mixing, it is entered using plastic pressuring process
Row sealing, the rectangular lithium ion battery that capacity is 50Ah is made.Electrochemical property test, knot are carried out to the lithium ion battery of preparation
Fruit shows that its initial energy density can reach 654mAh/g, and after 50 circulations, capability retention is more than 93%.
The battery outward appearance of preparation is detected, the results showed that, prepared using silicon-carbon cathode material provided by the invention
Battery, compared with graphite cathode battery, its volume can reduce 3.5%, and weight can mitigate 5.5%.
Embodiment 6
Silicon-carbon cathode material prepared by embodiment 3 is with acetylene black conductor and Kynoar binding agent by 90：5：5
Mass ratio is mixed, and is applied in copper foil current collector and battery core is made, and positive pole is used LiMn2O4 and acetylene black conductor and polyvinylidene fluoride
Alkene binding agent presses 90：5：Manufactured battery core in aluminum foil current collector is applied to after 5 mass ratio mixing, it is carried out using plastic pressuring process
Sealing, the rectangular lithium ion battery that capacity is 50Ah is made.Electrochemical property test is carried out to the lithium ion battery of preparation, as a result
Show, its initial energy density can reach 645mAh/g, and after 50 circulations, capability retention is more than 91%.
The battery outward appearance of preparation is detected, the results showed that, prepared using silicon-carbon cathode material provided by the invention
Battery, compared with graphite cathode battery, its volume can reduce 2.5%, and weight can mitigate 4.5%.
From above-described embodiment and comparative example, the present invention uses organosilicon cheap and easy to get as raw material, in the silicon of preparation
Carbon-carbon composite material surface has coated the preferable metal level of electric conductivity and metal oxide layer, and the silicon-carbon cathode material of preparation not only has
There is good electric conductivity, also there is longer cycle life.
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (5)
1. a kind of preparation method of silicon-carbon cathode material, including：
A) organo-silicon compound are mixed with reducing agent, reacts and obtains silicon-pyrolytic material；The temperature of the reaction be 600 DEG C~
900 DEG C, the time of the reaction is 2h~4h；
B) by step A) obtained silicon-pyrolytic material and graphite ball milling mixing, obtain silicon-pyrolysis carbon material；
C) by step B) obtained silicon-pyrolysis carbon material performs etching in acid solution, then with the salting liquid of metal ion
Mixing, deposited metal and its oxide, obtain silicon-carbon cathode material；
Any one or a few in silane coupler, silicone oil and silicones of the organo-silicon compound.
2. according to the method for claim 1, it is characterised in that the metal ion is selected from Fe2+、Fe3+、Sn2+And Ti4+In
Any one or a few.
3. according to the method for claim 1, it is characterised in that the reducing agent be selected from nickel-base catalyst, sodium borohydride and
Any one or a few in lithium aluminium hydride reduction.
4. according to the method for claim 1, it is characterised in that the acid solution includes appointing in nitric acid, hydrochloric acid or sulfuric acid
Meaning one kind and hydrofluoric acid and water.
5. according to the method for claim 1, it is characterised in that also include after the deposited metal and its oxide：To heavy
Material after product metal and its oxide is heated, and the temperature of the heating is 300 DEG C~1200 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310143242.1A CN103199225B (en) | 2013-04-23 | 2013-04-23 | Silicon-carbon cathode material, its preparation method and a kind of lithium ion battery |
Applications Claiming Priority (1)
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| DE112015006671T5 (en) * | 2015-07-07 | 2018-03-15 | Robert Bosch Gmbh | Silicon-based composition material with three-dimensional bonding network for lithium-ion batteries |
| CN106654185B (en) * | 2015-11-03 | 2020-05-22 | 宝山钢铁股份有限公司 | Silicon-based negative electrode active material for lithium ion battery and preparation method thereof |
| CN105655555B (en) * | 2016-01-13 | 2018-07-06 | 浙江天能能源科技股份有限公司 | A kind of Si-C composite material, preparation method and applications |
| KR20180093798A (en) * | 2017-02-13 | 2018-08-22 | 램 리써치 코포레이션 | Method to create air gaps |
| CN107507971A (en) * | 2017-08-29 | 2017-12-22 | 湖南格兰博智能科技有限责任公司 | A kind of silicon based anode material, preparation method and lithium ion battery |
| CN109390571A (en) * | 2018-10-09 | 2019-02-26 | 云南能投汇龙科技股份有限公司 | A kind of lithium ion battery silicon-carbon cathode material and preparation method |
| CN109935810A (en) * | 2019-03-07 | 2019-06-25 | 肇庆市华师大光电产业研究院 | A kind of preparation method of anode material of lithium-ion battery |
| CN113471399B (en) * | 2021-06-24 | 2022-11-01 | 湖北工程学院 | Preparation method and application of high-conductivity Si/C nano-film |
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