CN103199225A - Silicon carbon negative electrode material, preparation method of silicon carbon negative electrode material and lithium ion battery - Google Patents
Silicon carbon negative electrode material, preparation method of silicon carbon negative electrode material and lithium ion battery Download PDFInfo
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Abstract
The invention relates to a silicon carbon negative electrode material, a preparation method of the silicon carbon negative electrode material and a lithium ion battery. The preparation method comprises the steps of firstly mixing an organosilicon compound with a reducing agent, and reacting the organosilicon compound and the reducing agent to obtain a silicon pyrolysis material; then mixing the silicon pyrolysis material with graphite nodules to obtain a silicon pyrolysis carbon material; and etching the obtained silicon pyrolysis carbon material in a acid solution, mixing the etched silicon pyrolysis carbon material with a saline solution containing metal ions, and depositing metal and metal oxides to obtain the silicon carbon negative electrode material. According to the preparation method, the organosilicon, which is cheap and is easily available, is taken as a raw material, and the surface of the prepared composite silicon carbon material is covered with a metal layer with favorable electric conductivity and a metal oxide layer to form a conductive network, so that the electric conductivity of the silicon carbon negative electrode material is improved. Meanwhile, the metal and the metal oxides used for packing can efficiently lower the volume expansion and the mechanical stress in the charge and discharge processes of lithium ions, thereby prolonging the cycle life of the prepared composite material.
Description
Technical field
The present invention relates to the electrode material technical field, relate in particular to a kind of silicon-carbon cathode material, its preparation method and a kind of lithium ion battery.
Background technology
Lithium ion battery because have the operating voltage height, specific energy is big, self discharge is little and advantage such as low in the pollution of the environment, and is widely used in the civil and military field.Wherein negative material has material impact to fail safe, cycle life and the energy density of lithium battery, is the key factor of lithium ion battery technological progress.
At present, the widely used negative material of lithium ion battery is graphite material, it has cheaply superiority such as be easy to get, in light weight and thermal coefficient of expansion is little, but its theoretical lithium storage content only is 372mAh/g, along with the fast development of science and technology, can not satisfy lithium ion battery as the demand of energy-storage battery.In order to improve the capacitance of lithium ion battery, satisfy novel device to the demand of height ratio capacity battery, just need seek to have the electrode material of higher theoretical lithium storage content, perhaps graphite material is carried out modification, make it have higher theoretical lithium storage content, because silicon has the theoretical capacity value of 4200mAh/g, so silicon-carbon composite cathode material becomes the research focus.
Prior art discloses by chemical deposition silicon nanoparticle has been deposited in the graphite, the preparation Si-C composite material, and then lithium embedded the technology that graphite layers forms lithium ion battery negative material, but this technology, serious expansion very easily takes place in lithium ion volume in telescopiny, cause material after repeatedly discharging and recharging efflorescence can take place, electrode material can partly come off, and reduces battery life greatly; Simultaneously, the electric conductivity of silicon is also good not as material with carbon element, and the electric conductivity of the electrode material of feasible preparation is affected.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of silicon-carbon cathode material, its preparation method and a kind of lithium ion battery, and the silicon-carbon cathode material of preparation not only has excellent conducting performance, also has long cycle life.
The invention provides a kind of preparation method of silicon-carbon cathode material, comprising:
A) organo-silicon compound mixed with reducing agent, react and obtain silicon-pyrolytic material;
B) with steps A) silicon-pyrolytic material of obtaining mixes with the graphite ball milling, obtains silicon-RESEARCH OF PYROCARBON material;
C) with step B) silicon-RESEARCH OF PYROCARBON material of obtaining carries out etching in acid solution, and with the salt solution mix of metal ion, plated metal and oxide thereof obtain silicon-carbon cathode material then.
Preferably, described metal ion is selected from Fe
2+, Fe
3+, Sn
2+And Ti
4+In any one or a few.
Preferably, described reducing agent is selected from any one or a few in nickel-base catalyst, sodium borohydride and the lithium aluminium hydride reduction.
Preferably, described organo-silicon compound are selected from any one or a few in silane coupler, silicone oil and the silicones.
Preferably, described steps A) in, the temperature of described reaction is 600 ℃～900 ℃, the time of described reaction is 2h～4h.
Preferably, described acid solution comprises any one and hydrofluoric acid and the water in nitric acid, hydrochloric acid or the sulfuric acid.
Preferably, also comprise after the step of described plated metal and oxide thereof: the material behind plated metal and the oxide thereof is heated, obtain silicon-carbon cathode material; The temperature of described heating is 300 ℃～1200 ℃.
The present invention also provides a kind of silicon-carbon cathode material, for Si-C composite material surface clad and oxide thereof form.
Preferably, in described metal and the oxide thereof, described metal is any one or a few among Fe, Sn and the Ti.
The present invention also provides a kind of lithium ion battery, and its negative pole is for adopting the silicon-carbon cathode material of method preparation provided by the invention.
The present invention at first mixes organo-silicon compound with reducing agent, react and obtain silicon-pyrolytic material; Then it is mixed with the graphite ball milling, obtain silicon-RESEARCH OF PYROCARBON material; Again silicon-RESEARCH OF PYROCARBON the material that obtains is carried out etching in acid solution, with the salt solution mix of metal ion, plated metal and oxide thereof obtain silicon-carbon cathode material then.It is raw material that the present invention adopts organosilicon cheap and easy to get, has coated better conductivity metal level and metal oxide layer on the Si-C composite material surface of preparation, forms conductive network, has improved the electric conductivity of material; Simultaneously, the metal that coats and oxide skin(coating) can effectively reduce volumetric expansion and the mechanical stress in the lithium ion charge and discharge process, make the composite material of preparation have long cycle life.
Adopt the metal-modified silicon-carbon cathode material of the present invention's preparation to prepare battery, and carry out Performance Detection, the result shows that the battery primary power density of preparation can reach 623mAh/g, and after 50 circulations, capability retention surpasses 92%; And its volume and weight is compared with the battery of graphite material preparation, can optimize about 12% and 11% respectively.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of the silicon-carbon cathode material of the embodiment of the invention 1 preparation;
Fig. 2 is the discharge curve of the battery of the embodiment of the invention 4 preparations;
Fig. 3 is the cyclic curve figure of the battery of the embodiment of the invention 4 preparations.
Embodiment
The invention provides a kind of preparation method of silicon-carbon cathode material, comprising:
A) organo-silicon compound mixed with reducing agent, react and obtain silicon-pyrolytic material;
B) with steps A) silicon-pyrolytic material of obtaining mixes with the graphite ball milling, obtains silicon-RESEARCH OF PYROCARBON material;
C) with step B) silicon-RESEARCH OF PYROCARBON material of obtaining carries out etching in acid solution, and with the salt solution mix of metal ion, plated metal and oxide thereof obtain silicon-carbon cathode material then.
The present invention at first mixes organo-silicon compound with reducing agent, react and obtain silicon-pyrolytic material; Then it is mixed with the graphite ball milling, obtain silicon-RESEARCH OF PYROCARBON material; Again silicon-RESEARCH OF PYROCARBON the material that obtains is carried out etching in acid solution, with the salt solution mix of metal ion, plated metal and oxide thereof obtain silicon-carbon cathode material then.It is raw material that the present invention adopts organosilicon cheap and easy to get, has coated better conductivity metal level and metal oxide layer on the Si-C composite material surface of preparation, forms conductive network, has improved the electric conductivity of material; Simultaneously, the metal that coats and oxide skin(coating) thereof can effectively reduce volumetric expansion and the mechanical stress in the lithium ion charge and discharge process, make the composite material of preparation have long cycle life.
The present invention at first mixes organo-silicon compound with reducing agent, react and obtain silicon-pyrolytic material.Described organo-silicon compound preferably adopt any one or a few in silane coupler, silicone oil and the silicones; More preferably adopt silane coupler; Described reducing agent is preferably any one or a few in nickel-base catalyst, sodium borohydride and the lithium aluminium hydride reduction; Nickel-base catalyst more preferably.The present invention does not all have specific (special) requirements to the source of described organo-silicon compound and reducing agent, can be for generally commercially available.Among the present invention, the temperature of described reaction is preferably 600 ℃～900 ℃, more preferably 750 ℃～850 ℃; The time of described reaction is 2h～4h, more preferably 2.5h～3.5h.Described reaction is preferably carried out under the protection of inert gas, and described inert gas is preferably nitrogen.
After obtaining silicon-pyrolytic material, it is mixed with the graphite ball milling, obtain silicon-RESEARCH OF PYROCARBON material; The mass ratio of described silicon-pyrolytic material and graphite is preferably 1:(1～3), 1:(1.5～2.5 more preferably); The present invention there is no specific (special) requirements to the source of described graphite, can be for generally commercially available.
Then, the silicon-RESEARCH OF PYROCARBON material that obtains is carried out etching in acid solution, described acid solution preferably includes any one and hydrofluoric acid and the water in nitric acid, hydrochloric acid or the sulfuric acid; The mass ratio of described nitric acid, hydrochloric acid or sulfuric acid and hydrofluoric acid, water is preferably 1:(2～4): (5～7); The present invention does not have specific (special) requirements to the method for described etching, can be lithographic method well known to those skilled in the art, and the present invention is preferred, can adopt the method for stirring or ultrasonic concussion etching; The time of described etching is preferably 2min～30min; After described silicon-RESEARCH OF PYROCARBON material carried out etching, preferred, adopt distilled water that it is cleaned, the present invention does not have specific (special) requirements to the method for described cleaning, can be general cleaning method, and is preferred, the method that adopts the ultrasonic concussion of deionized water to clean; Filter the silicon-RESEARCH OF PYROCARBON material that can obtain after the surface treatment with cleaning material later.
With the salt solution mix of the silicon after the surface treatment that obtains-RESEARCH OF PYROCARBON material and metal ion, plated metal and oxide thereof can obtain silicon-carbon cathode material.In the salting liquid of described metal ion, described metal ion is preferably Fe
2+, Fe
3+, Sn
2+And Ti
4+In any one or a few; The present invention is in the described salting liquid, and the kind of anion there is no particular determination, can be sulfate radical, nitrate anion, chloride ion, acetate; The salting liquid of described metal ion is preferably any one or a few in ferric sulfate, ferrous sulfate, STANNOUS SULPHATE CRYSTALLINE, titanium sulfate, ferrous nitrate, ferric nitrate, nitric acid tin, four Titanium Nitrates, frerrous chloride, iron chloride, stannic chloride, titanium tetrachloride, ferrous acetate, ferric acetate, tin acetate and the acetic acid titanium, more preferably any one or a few in ferrous sulfate, ferric nitrate, STANNOUS SULPHATE CRYSTALLINE, titanium sulfate and the titanium tetrachloride; The concentration of the salting liquid of described metal ion is preferably 1mol/L～5mol/L; It contains Fe
2+, Fe
3+, Sn
2+And Ti
4+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 Fe
2+, Fe
3+, Sn
2+And Ti
4+Can not be 0 simultaneously; In described plated metal and the oxide thereof, described metal is preferably any one or a few among Fe, Sn and the Ti, and preferred, described metal and oxide thereof can be selected from Fe and Fe
2O
3, perhaps be selected from Sn and SnO, perhaps be selected from Ti and TiO
2, perhaps be selected from Fe, Fe
2O
3, Sn and SnO; Perhaps be selected from Fe, Fe
2O
3, Ti and TiO
2Perhaps be selected from Sn, SnO, Ti and TiO
2Perhaps be selected from Fe, Fe
2O
3, Sn, SnO, Ti and TiO
2The ratio of the gross mass of the gross mass of the gross mass of described deposited iron and oxide thereof and tin and oxide thereof and titanium and oxide thereof is preferably (0～0.8): (0～1): (0～1), and iron and oxide, tin and oxide thereof and titanium and oxide thereof can not be 0 simultaneously.
The present invention can form conductive network at silicon-carbon cathode material surface deposition metal and metal oxide layer, improves the electric conductivity of material; And described metal and metal oxide layer can improve the lithium storage content of negative material greatly, make material have higher capacitance; Simultaneously, the metal that coats and oxide skin(coating) thereof can effectively reduce volumetric expansion and the mechanical stress in the lithium ion charge and discharge process, make the composite material of preparation have long cycle life.
Behind plated metal and the oxide thereof, preferred, also comprise the material behind plated metal and the oxide thereof is heated, obtain silicon-carbon cathode material; The temperature of described heating is preferably 300 ℃～1200 ℃, more preferably 500 ℃～1000 ℃; The time of described heating is preferably 1h～3h; 1.5h～2.5h more preferably.Preferably, described heating is carried out in reducibility gas, and the present invention there is no particular determination to described reducibility gas, can be reducibility gas well known to those skilled in the art, is preferably mist or the CO (carbon monoxide converter) gas of hydrogen and nitrogen; The volume ratio of described hydrogen and nitrogen is preferably (2～3): 1.Material behind plated metal and the oxide thereof is heated, be conducive to increase the binding ability of metal ion and silicon-RESEARCH OF PYROCARBON material, improve the cycle performance of material.
The present invention also provides a kind of silicon-carbon cathode material, for Si-C composite material surface clad and oxide thereof form.In described metal and the oxide thereof, described metal is preferably any one or a few of Fe, Sn and Ti; Preferably, described metal and oxide thereof can be selected from Fe and Fe
2O
3, Sn and SnO, Ti and TiO
2In any one or a few, and Fe and Fe
2O
3Must exist simultaneously, Sn and SnO must exist simultaneously, Ti and TiO
2Must exist simultaneously; The ratio of the gross mass of the gross mass of the gross mass of described iron and oxide thereof and tin and oxide thereof and titanium and oxide thereof is preferably (0～0.8): (0～1): (0～1), and iron and oxide, tin and oxide thereof and titanium and oxide thereof can not be 0 simultaneously.
Adopt scanning electron microscopy that silicon-carbon cathode material provided by the invention is carried out pattern and detect, the result shows that silicon-carbon cathode material provided by the invention is micron-scale, and is the lamella packed structures; The pore-size distribution test result shows that silicon-carbon cathode material diameter provided by the invention is 5～10 microns, and has bigger specific area.
The present invention also provides a kind of battery, and its negative pole is according to the silicon-carbon cathode material of method preparation provided by the invention or adopts silicon-carbon cathode material provided by the invention.The present invention there is no specific (special) requirements to the positive electrode of described battery, can be cell positive material well known to those skilled in the art, and the present invention is preferably LiMn2O4 or LiFePO4.
Concrete, silicon-carbon cathode material is mixed with conductive agent and binding agent, be applied to and make the negative electricity core on the Copper Foil collector; Simultaneously positive electrode is mixed with conductive agent and binding agent, be applied to and make anodal electric core on the aluminum foil current collector; The present invention there is no specific (special) requirements to described conductive agent and binding agent, can be conductive agent and the binding agent that can be used for preparing battery well known to those skilled in the art, the present invention is preferred, described conductive agent is acetylene black, carbon black or graphite, and described binding agent is Kynoar, polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose or polyurethane; The weight ratio of described negative material or positive electrode and conductive agent, binding agent is preferably (80～90): (5～10); (5～10), and each constituent content summation is 100; Negative electricity core and anodal electric core with preparation uses plastic pressuring process to seal then, namely can be made into lithium ion battery.The capacitance of described lithium ion battery is 10Ah～200Ah.
Battery to preparation carries out Performance Detection, and the result shows that its primary power density can reach 623mAh/g, and after 50 circulations, capability retention surpasses 92%, and its volume and weight has optimized about 12% and 10.7% respectively.
It is raw material that the present invention adopts organosilicon cheap and easy to get, has coated better conductivity metal level and metal oxide layer on the Si-C composite material surface of preparation, forms conductive network, has improved the electric conductivity of material; And described metal and metal oxide layer can improve the lithium storage content of negative material greatly, make material have higher capacitance; Simultaneously, the metal that coats and oxide skin(coating) thereof can effectively reduce volumetric expansion and the mechanical stress in the lithium ion charge and discharge process, make the composite material of preparation have long cycle life.And, the material of preparation is nanoscale, can reduce the absolute change value of material volume in the conducting process, shorten the evolving path of lithium ion, thereby improve the electrical conductivity performance of prepared silicon-carbon cathode material, therefore, silicon-carbon cathode material provided by the invention, not only have excellent conducting performance, also have long cycle life.
In order to further specify the present invention, below in conjunction with embodiment silicon-carbon cathode material provided by the invention and preparation method thereof is described in detail.
Embodiment 1
Silane coupler 1g is mixed with the 0.05g nickel-base catalyst, after stirring, under protection of nitrogen gas, under 800 ℃ condition, add thermal response 3h, obtain silicon-pyrolytic material; After silicon-pyrolytic material 1g of obtaining and graphite 1.5g ball milling mixed, obtain silicon-RESEARCH OF PYROCARBON material; With the silicon-RESEARCH OF PYROCARBON dispersion of materials etching 4min in acid solution that obtains, described acid solution is that mass ratio is the mixed solution of 65wt% hydrofluoric acid, 50wt% nitric acid and the water of 10:30:60, behind the ultrasonic concussion etching 4min, material is removed surface acid solution with the ultrasonic concussion cleaning of distilled water, filtration obtains solid, the solid dispersed that obtains in the copperas solution of concentration 2mol/L, is made Fe and Fe
2O
3Being deposited on described silicon-RESEARCH OF PYROCARBON material surface, is in the mist of the hydrogen of 3:1 and nitrogen in volume ratio then, heats 1h under 400 ℃ temperature conditions, obtains silicon-carbon cathode material.
By scanning electron microscopy the silicon-carbon cathode material for preparing is carried out pattern and detect, experimental result is seen Fig. 1, and Fig. 1 is the scanning electron microscope diagram of the silicon-carbon cathode material of embodiment 1 preparation.As shown in Figure 1, silicon-carbon cathode material provided by the invention is that micron-sized lamella is piled up material.
Silicon-carbon cathode material to preparation carries out the pore-size distribution test, and the result shows that the diameter of the silicon-carbon cathode material of the present invention's preparation is 9.486 μ m, and its specific area is 23.947m
2/ g, density is 0.54g/cm
3
Its component is detected, and the result shows that the silicon-carbon cathode material of the present invention's preparation comprises: the carbon of 75.7wt%, the silicon of 21.2wt% and the iron of 2.8wt% and 0.3wt% di-iron trioxide.
Embodiment 2
Silane coupler 1g is mixed with the 0.05g nickel-base catalyst, after stirring, under protection of nitrogen gas, under 800 ℃ condition, add thermal response 3h, obtain silicon-pyrolytic material; After silicon-pyrolytic material 1g of obtaining and graphite 1.5g ball milling mixed, obtain silicon-RESEARCH OF PYROCARBON material; With silicon-RESEARCH OF PYROCARBON dispersion of materials of obtaining in acid solution, ultrasonic concussion etching 10min, described acid solution is that mass ratio is the mixed solution of hydrofluoric acid, nitric acid and the water of 10:30:60, behind the etching 10min, after the ultrasonic concussion cleaning of material usefulness distilled water, filtration obtains solid, with the solid dispersed that obtains in the STANNOUS SULPHATE CRYSTALLINE solution of concentration 2mol/L, make Sn and SnO be deposited on described silicon-RESEARCH OF PYROCARBON material surface, be in the mist of the hydrogen of 2:1 and nitrogen in volume ratio then, under 800 ℃ temperature conditions, heat 1h, obtain silicon-carbon cathode material.
By scanning electron microscopy the silicon-carbon cathode material for preparing is carried out pattern and detect, experimental result shows that silicon-carbon cathode material provided by the invention is that micron-sized lamella is piled up material.
Silicon-carbon cathode material to preparation carries out the pore-size distribution test, and the result shows that the diameter of the silicon-carbon cathode material of the present invention's preparation is 5.452 μ m, and its specific area is 17.655m
2/ g, density is 0.46g/cm
3
Its component is detected, and the result shows that the silicon-carbon cathode material of the present invention's preparation comprises: the carbon of 77.6wt%, the silicon of 19.8wt% and the tin of 2.0wt% and 0.6wt% tin oxide.
Embodiment 3
Silane coupler 1g is mixed with the 0.05g nickel-base catalyst, after stirring, under protection of nitrogen gas, under 800 ℃ condition, add thermal response 3h, obtain silicon-pyrolytic material; After silicon-pyrolytic material 1g of obtaining and graphite 1.5g ball milling mixed, obtain silicon-RESEARCH OF PYROCARBON material; With silicon-RESEARCH OF PYROCARBON dispersion of materials of obtaining in acid solution, ultrasonic concussion etching 2min, described acid solution is that mass ratio is the mixed solution of hydrofluoric acid, nitric acid and the water of 10:30:60, behind the etching 2min, after the ultrasonic concussion cleaning of material usefulness distilled water, filtration obtains solid, and the solid dispersed that obtains in the titanium sulfate solution of concentration 2mol/L, is made Ti and TiO
2Being deposited on described silicon-RESEARCH OF PYROCARBON material surface, is in the mist of the hydrogen of 2:1 and nitrogen in volume ratio then, heats 1h under 1000 ℃ temperature conditions, obtains silicon-carbon cathode material.
By scanning electron microscopy the silicon-carbon cathode material for preparing is carried out pattern and detect, experimental result shows that silicon-carbon cathode material provided by the invention is that micron-sized lamella is piled up material.
Silicon-carbon cathode material to preparation carries out the pore-size distribution test, and the result shows that the diameter of the silicon-carbon cathode material of the present invention's preparation is 6.722 μ m, and its specific area is 15.782m
2/ g, density is 0.54g/cm
3
Its component is detected, and the result shows that the silicon-carbon cathode material of the present invention's preparation comprises: the carbon of 77.5wt%, the silicon of 20.1wt% and the titanium of 2.0wt% and 0.4wt% titanium dioxide.
Embodiment 4
The silicon-carbon cathode material of embodiment 1 preparation and acetylene black conductive agent and the Kynoar binding agent mass ratio by 90:5:5 is mixed, be applied to and make electric core on the Copper Foil collector, the anodal employing is applied to the electric core of making on the aluminum foil current collector after LiMn2O4 and acetylene black conductive agent and Kynoar binding agent mixed by the mass ratio of 90:5:5, use plastic pressuring process that it is sealed, the capacity of making is the rectangular lithium ion battery of 50Ah.Lithium ion battery to preparation carries out electrochemical property test, and test result is seen Fig. 2 and Fig. 3.Fig. 2 is the discharge curve of the battery of the embodiment of the invention 4 preparations; Fig. 3 is the cyclic curve figure of the battery of the embodiment of the invention 4 preparations; By Fig. 2 and Fig. 3 as can be known, adopt the battery of silicon-carbon cathode material preparation provided by the invention, its primary power density can reach 623mAh/g, and after 50 circulations, capability retention surpasses 92%.
Battery outward appearance to preparation detects, and the results are shown in Table 1, and table 1 is volume of battery, the weight contrast of the embodiment of the invention 4 and comparative example 1 preparation; As shown in Table 1, adopt the battery of silicon-carbon cathode material preparation provided by the invention, compare with the graphite cathode battery, its volume can reduce 12%, and weight can alleviate 10.7%.
Comparative example 1
Native graphite 10g is mixed with phenolic resins 2g, and 150 ℃ are carried out sintering, then system is cooled to room temperature (25 ℃) after, adopt the spherical grinding machine that product is pulverized, then the product after pulverizing is sieved, obtain the graphite cathode material of coating modification.
Adopting the graphite cathode material of preparation is negative pole, it is mixed with acetylene black conductive agent and the Kynoar binding agent mass ratio by 90:5:5, be applied to and make electric core on the Copper Foil collector, the anodal employing is applied to the electric core of making on the aluminum foil current collector after LiMn2O4 and acetylene black conductive agent and Kynoar binding agent mixed by the mass ratio of 90:5:5, use plastic pressuring process that it is sealed, the capacity of making is the rectangular lithium ion battery of 50Ah.Battery outward appearance to preparation detects, and the results are shown in Table 1, and table 1 is volume of battery, the weight contrast of the embodiment of the invention 4 and comparative example 1 preparation.
The volume of battery of table 1 embodiment of the invention 4 and comparative example 1 preparation, 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 resins 2g, and 150 ℃ are carried out sintering, add silane coupler 3g ball milling then and mix, and make Si-C composite material.
Adopting the Si-C composite material of preparation is negative pole, it is mixed with acetylene black conductive agent and the Kynoar binding agent mass ratio by 90:5:5, be applied to and make electric core on the Copper Foil collector, the anodal employing is applied to the electric core of making on the aluminum foil current collector after LiMn2O4 and acetylene black conductive agent and Kynoar binding agent mixed by the mass ratio of 90:5:5, use plastic pressuring process that it is sealed, the capacity of making is the rectangular lithium ion battery of 50Ah.Battery to preparation carries out electrochemical property test, and the result shows that its primary power density is 732mAh/g; After 50 circulations, capability retention is 67%.
Embodiment 5
The silicon-carbon cathode material of embodiment 2 preparation and acetylene black conductive agent and the Kynoar binding agent mass ratio by 90:5:5 is mixed, be applied to and make electric core on the Copper Foil collector, the anodal employing is applied to the electric core of making on the aluminum foil current collector after LiFePO4 and acetylene black conductive agent and Kynoar binding agent mixed by the mass ratio of 90:5:5, use plastic pressuring process that it is sealed, the capacity of making is the rectangular lithium ion battery of 50Ah.Lithium ion battery to preparation carries out electrochemical property test, and the result shows that its primary power density can reach 654mAh/g, and after 50 circulations, capability retention surpasses 93%.
Battery outward appearance to preparation detects, and the result shows, adopts the battery of silicon-carbon cathode material preparation provided by the invention, compares with the graphite cathode battery, and its volume can reduce 3.5%, and weight can alleviate 5.5%.
Embodiment 6
The silicon-carbon cathode material of embodiment 3 preparation and acetylene black conductive agent and the Kynoar binding agent mass ratio by 90:5:5 is mixed, be applied to and make electric core on the Copper Foil collector, the anodal employing is applied to the electric core of making on the aluminum foil current collector after LiMn2O4 and acetylene black conductive agent and Kynoar binding agent mixed by the mass ratio of 90:5:5, use plastic pressuring process that it is sealed, the capacity of making is the rectangular lithium ion battery of 50Ah.Lithium ion battery to preparation carries out electrochemical property test, and the result shows that its primary power density can reach 645mAh/g, and after 50 circulations, capability retention surpasses 91%.
Battery outward appearance to preparation detects, and the result shows, adopts the battery of silicon-carbon cathode material preparation provided by the invention, compares with the graphite cathode battery, and its volume can reduce 2.5%, and weight can alleviate 4.5%.
By above-described embodiment and comparative example as can be known, it is raw material that the present invention adopts organosilicon cheap and easy to get, Si-C composite material surface in preparation has coated better conductivity metal level and metal oxide layer, the silicon-carbon cathode material of preparation not only has excellent conducting performance, also has long cycle life.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of claim of the present invention.
Claims (10)
1. the preparation method of a silicon-carbon cathode material comprises:
A) organo-silicon compound mixed with reducing agent, react and obtain silicon-pyrolytic material;
B) with steps A) silicon-pyrolytic material of obtaining mixes with the graphite ball milling, obtains silicon-RESEARCH OF PYROCARBON material;
C) with step B) silicon-RESEARCH OF PYROCARBON material of obtaining carries out etching in acid solution, and with the salt solution mix of metal ion, plated metal and oxide thereof obtain silicon-carbon cathode material then.
2. method according to claim 1 is characterized in that, described metal ion is selected from Fe
2+, Fe
3+, Sn
2+And Ti
4+In any one or a few.
3. method according to claim 1 is characterized in that, described reducing agent is selected from any one or a few in nickel-base catalyst, sodium borohydride and the lithium aluminium hydride reduction.
4. method according to claim 1 is characterized in that, described organo-silicon compound are selected from any one or a few in silane coupler, silicone oil and the silicones.
5. method according to claim 1 is characterized in that, described steps A) in, the temperature of described reaction is 600 ℃～900 ℃, the time of described reaction is 2h～4h.
6. method according to claim 1 is characterized in that, described acid solution comprises any one and hydrofluoric acid and the water in nitric acid, hydrochloric acid or the sulfuric acid.
7. method according to claim 1 is characterized in that, also comprises behind described plated metal and the oxide thereof: the material behind plated metal and the oxide thereof is heated, obtain silicon-carbon cathode material; The temperature of described heating is 300 ℃～1200 ℃.
8. silicon-carbon cathode material is for Si-C composite material surface clad and oxide thereof form.
9. silicon-carbon cathode material according to claim 8 is characterized in that, in described metal and the oxide thereof, described metal is any one or a few among Fe, Sn and the Ti.
10. lithium ion battery, its negative pole are silicon-carbon cathode material or claim 8 or the 9 described silicon-carbon cathode materials of any described method preparation of claim 1～7.
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| CN113471399A (en) * | 2021-06-24 | 2021-10-01 | 湖北工程学院 | Preparation method and application of high-conductivity Si/C nano-film |
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