CN103000383A - Super capacitance battery and preparation method thereof - Google Patents
Super capacitance battery and preparation method thereof Download PDFInfo
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- CN103000383A CN103000383A CN2011102737540A CN201110273754A CN103000383A CN 103000383 A CN103000383 A CN 103000383A CN 2011102737540 A CN2011102737540 A CN 2011102737540A CN 201110273754 A CN201110273754 A CN 201110273754A CN 103000383 A CN103000383 A CN 103000383A
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Abstract
Disclosed is a super capacitance battery. An anode comprises an anode current collector and an anode material coated on the anode current collector, the anode material comprises an anode active material, a first binder and a first conductive agent, the anode active material is composed of a carbon material and a lithium ion material, the content of the carbon material in the anode active material is larger than or equal to 70% and smaller than 100%, a cathode comprises a cathode current collector and a cathode material coated on the cathode current collector, the cathode material comprises a cathode active material, a second binder and a second conductive agent, the cathode active material is composed of a silicon mixture and graphene according to the mass ratio of 1-20:80-99, and the silicon mixture is composed of monatomic silicon and silicon dioxide according to the mass ratio of 1:19-19:1. The cathode of the super capacitance battery is provided with a low potential platform, so that average working voltage of the super capacitance battery is increased, and the super capacitance battery has high-ratio power characteristics and high-ratio energy characteristics. In addition, the invention further provides a preparation method for the super capacitance battery.
Description
[technical field]
The present invention relates to capacitor area, particularly a kind of super capacitance cell and preparation method thereof.
[background technology]
The nineties in 20th century, to the exploitation of electric automobile and to the demand of pulse power supply, more stimulated the research of people to electrochemical capacitor.The specific energy of electrochemical capacitor is still lower at present, and the specific power of battery is lower, and people are just attempting to address this problem from two aspects: (1) unites use with battery and ultracapacitor, during normal operation, provides required power by battery; Start or when needing heavy-current discharge, then provided by capacitor, can improve on the one hand the bad shortcoming of cryogenic property of battery; Can solve the application scenario for the higher pulse current of power requirement, such as GSM, GPRS etc.Capacitor and battery are united use and can be extended the life of a cell, but this will increase the annex of battery, disagree with the developing direction such as short and small frivolous of present energy device.(2) utilize the principle of electrochemical capacitor and battery, the exploitation mixed capacitor is as new energy storage unit.
It is so-called fake capacitance device or the title pseudo-capacitance device (Pseudo-capacitor) of electrode material that nineteen ninety Giner company has released metal oxide containing precious metals.For further improving the specific energy of electrochemical capacitor, nineteen ninety-five, D.A.Evans etc. have proposed ideal polarized electrode and faraday's reaction electrode are combined the concept that consists of mixed capacitor (Electrochemical Hybrid Capacitor, EHC or be called Hybrid capacitor).1997, ESMA company disclosed the concept of NiOOH/AC mixed capacitor, had disclosed the new technology of accumulator material and electrochemical capacitor combination of materials.Calendar year 2001, G.G.Amatucci has reported the Li of organic system lithium ion battery material and active carbon combination
4Ti
5O
12/ AC electrochemical mixed capacitor is another milestone of electrochemical mixed capacitor development.Yet there is the problem that power density is low and energy density is low in this electrochemical mixed capacitor.
[summary of the invention]
Based on this, be necessary to provide a kind of capacitor batteries that has high-specific-power characteristic and high-energy-density characteristic concurrently.
A kind of super capacitance cell, comprise positive pole, negative pole, the barrier film between described positive pole and negative pole and electrolyte, described positive pole, negative pole and barrier film are soaked in the described electrolyte, described positive pole comprises plus plate current-collecting body and is coated on positive electrode on the described plus plate current-collecting body, described positive electrode comprises positive electrode active materials, the first binding agent and the first conductive agent, described positive electrode active materials is comprised of carbon materials and lithium ion material, and the content of carbon materials is more than or equal to 70% and less than 100% described in the described positive electrode active materials; Described negative pole comprises negative current collector and is coated on negative material on the described negative current collector, described negative material comprises negative active core-shell material, the second binding agent and the second conductive agent, described negative active core-shell material is comprised of silicon mixture and Graphene, the mass ratio of described silicon mixture and Graphene is 1～20: 80～99, described silicon mixture is comprised of elemental silicon and silicon dioxide, and the mass ratio of described elemental silicon and silicon dioxide is 1: 19～19: 1.
In a preferred embodiment, the mass ratio of described positive electrode active materials, the first binding agent and the first conductive agent is 85～90: 5～10: 5～10; The mass ratio of described negative active core-shell material, the second binding agent and the second conductive agent is 85～90: 5～10: 5～10.
In a preferred embodiment, described lithium ion material is LiFePO4, lithium nickel cobalt manganese oxygen, lithium cobalt oxygen, lithium manganese oxygen, Li-Ni-Mn-O, lithium-nickel-cobalt-oxygen, lithium vanadium oxygen or ferric metasilicate lithium.
In a preferred embodiment, described the first conductive agent and the second conductive agent are acetylene black, conductive black or carbon nano-tube; Described the first binding agent and the second binding agent are Kynoar.
In addition, also be necessary to provide a kind of preparation method who has the capacitor batteries of high-specific-power characteristic and high-energy-density characteristic concurrently.
A kind of preparation method of super capacitance cell comprises the steps:
Step 1: carbon materials is mixed with into positive electrode active materials with the lithium ion material, the content of carbon materials is more than or equal to 70% and less than 100% described in the described positive electrode active materials, be that 1～20: 80～99 silicon mixture is mixed with into negative active core-shell material with Graphene with mass ratio, described silicon mixture is that 1: 19～19: 1 elemental silicon and silicon dioxide forms by mass ratio;
Step 2: described positive electrode active materials and the first binding agent, the first conductive agent and the first solvent are mixed with anode sizing agent, described negative active core-shell material and the second binding agent, the second conductive agent and the second solvent are mixed with cathode size;
Step 3: described anode sizing agent is coated on the plus plate current-collecting body, then dry, roll film, cut and be made into positive pole, described cathode size is coated on the negative current collector, then dry, roll film, cut and be made into negative pole; And
Step 4: with described positive pole, barrier film and negative pole fit successively the assembling after be soaked in the electrolyte, obtain described super capacitance cell.
In a preferred embodiment, in the step 1, the preparation process of negative active core-shell material also comprises the steps: SiO 2 powder and graphite oxide powder are mixed with mixture, described mixture ball milling is placed on the speed with 10～100 ℃/minute is warming up to 200～1200 ℃ under the reducing atmosphere, heat and obtained mixture of powders in 1～10 hour, then described mixture of powders is cooled to room temperature in reducing atmosphere, obtains described negative active core-shell material.
In a preferred embodiment, in the step 2, the mass ratio of described positive electrode active materials, the first binding agent and the first conductive agent is 85～90: 5～10: 5～10; The mass ratio of described negative active core-shell material, the second binding agent and the second conductive agent is 85～90: 5～10: 5～10.
In a preferred embodiment, in the step 2, described the first solvent and the second solvent are 1-METHYLPYRROLIDONE, the viscosity of described anode sizing agent and cathode size be 1500～3000 Newton-seconds/square metre.
In a preferred embodiment, in the step 3, described plus plate current-collecting body is aluminium foil, and described negative current collector is Copper Foil.
In a preferred embodiment, in the step 4, described electrolyte is that lithium-ion electrolyte salt and non-aqueous organic solvent are formulated.
The negative pole of above-mentioned super capacitance cell adopts the negative active core-shell material that consists of elemental silicon, silicon dioxide and Graphene, so that negative pole has low current potential platform, cause the average working voltage of super capacitance cell to be higher than traditional double electric layer capacitor, and silicon has characteristics capacious, the theoretical capacity 4200mAh/g of silicon, be far longer than the capacity 372mAh/g of graphite cathode, thereby the energy density of system is risen.The conductivity that grapheme material is good, grapheme material and elemental silicon and silicon dioxide is compound after, Graphene can well pass to electronics on the silicon materials, silicon materials are dispersed in and are conducive to the stable of material in the graphene sheet layer structure simultaneously.And in the silicon mixture that elemental silicon and silicon dioxide form, the existence of silicon dioxide can effectively slow down the capacity attenuation of elemental silicon, because it does not react silicon dioxide, also can slow down the capacity attenuation that elemental silicon causes because of volumetric expansion in charge and discharge process, thereby can be good at cushioning the expansion of elemental silicon in system, so that above-mentioned super capacitance cell has high-specific-power characteristic and high-energy-density characteristic concurrently.
[description of drawings]
Fig. 1 is the super capacitance cell preparation method flow chart of an execution mode;
Fig. 2 is the constant current charge-discharge curve chart of the super capacitance cell of embodiment 1.
[embodiment]
The below mainly is described in further detail super capacitance cell and preparation method thereof in conjunction with the drawings and the specific embodiments.
The super mixed capacitor of one execution mode comprises positive pole, negative pole, the barrier film between positive pole and negative pole and electrolyte, and positive pole, negative pole and barrier film are soaked in the electrolyte.
The anodal positive pole commonly used that can use for ultracapacitor.Positive pole comprises plus plate current-collecting body and is coated on positive electrode on the plus plate current-collecting body, positive electrode comprises positive electrode active materials, the first binding agent and the first conductive agent, positive electrode active materials is comprised of carbon materials and lithium ion material, and the content of carbon materials is more than or equal to 70% and less than 100% in the positive electrode active materials.The mass ratio of positive electrode active materials, the first binding agent and the first conductive agent is 85～90: 5～10: 5～10.Carbon materials is preferably active carbon, carbon aerogels, carbon nano-tube or pyrolytic carbon.The lithium ion material is LiFePO4, lithium nickel cobalt manganese oxygen, lithium cobalt oxygen, lithium manganese oxygen, Li-Ni-Mn-O, lithium-nickel-cobalt-oxygen, lithium vanadium oxygen or ferric metasilicate lithium.The main carbon materials that adopts comes stored energy with electric double layer mechanism in the positive pole, takes off embedding mechanism with respect to one of the ion embedding of lithium ion battery, can carry out high-power output.
Negative pole comprises negative current collector and is coated on negative material on the negative current collector that negative material comprises negative active core-shell material, the second binding agent and the second conductive agent.The mass ratio of negative active core-shell material, the second binding agent and the second conductive agent is 85～90: 5～10: 5～10.Negative active core-shell material is that 1～20: 80～99 silicon mixture and Graphene form by mass ratio, and the silicon mixture is comprised of elemental silicon and silicon dioxide, and the mass ratio of elemental silicon and silicon dioxide is 1: 19～19: 1.The compound negative pole that is prepared into of elemental silicon, silicon dioxide and Graphene, so that negative pole has low current potential platform, increased the average working voltage of super capacitance cell, in the silicon mixture that elemental silicon and silicon dioxide form, the existence of silicon dioxide can effectively slow down the capacity attenuation of elemental silicon, because it does not react silicon dioxide, can slow down the capacity attenuation that elemental silicon causes because of volumetric expansion in charge and discharge process yet, thereby can be good at cushioning the expansion of elemental silicon in system.
In a preferred embodiment, the first binding agent and the second binding agent are preferably Kynoar (PVDF); The first conductive agent and the second conductive agent are preferably acetylene black, the common conductive agents such as conductive black (for example, conductive black supperP) or carbon nano-tube.
In a preferred embodiment, barrier film adopts lithium ion battery pp barrier film commonly used.
In preferred embodiment, electrolyte is that lithium-ion electrolyte salt and non-aqueous organic solvent are formulated.Lithium-ion electrolyte salt is preferably LiPF6, LiBF
4, LiBOB, LiCF
3SO
3, LiN (SO
2CF
3) or LiAsF
6Non-aqueous organic solvent is preferably one or more in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, ethylene sulfite, propylene sulfite, butylene, r-butyrolactone, methyl ethyl carbonate alkene ester, methyl propyl carbonate, ethyl acetate and the acetonitrile.
As shown in Figure 1, the preparation method of above-mentioned super capacitance cell comprises the steps:
Step S1, carbon materials is mixed with into positive electrode active materials with the lithium ion material, the content of carbon materials is more than or equal to 70% and less than 100% described in the described positive electrode active materials, be that 1～20: 80～99 silicon mixture is mixed with into negative active core-shell material with Graphene with mass ratio, the silicon mixture is that 1: 19～19: 1 elemental silicon and silicon dioxide forms by mass ratio.In the present embodiment, the preparation process of negative active core-shell material also comprises the steps: SiO 2 powder and graphite oxide powder are mixed with mixture, with the mixture ball milling be placed on reducing atmosphere tube furnace in slowly be warming up to 200～1200 ℃ with 10～100 ℃/minute speed, heat and obtained mixture of powders in 1～10 hour, then in reducing atmosphere, cool to mixture of powders with the furnace room temperature, obtain negative active core-shell material.Reducing atmosphere is preferably the gaseous mixture atmosphere that percent by volume is 5: 95 hydrogen and argon gas.
Step S2 is mixed with anode sizing agent with positive electrode active materials and the first binding agent, the first conductive agent and the first solvent, and negative active core-shell material and the second binding agent, the second conductive agent and the second solvent are mixed with cathode size.The mass ratio of positive electrode active materials, the first binding agent and the first conductive agent is preferably 85～90: 5～10: 5～10.The mass ratio of negative active core-shell material and the second binding agent, the second conductive agent is preferably 85～90: 5～10: 5～10.The first solvent and the second solvent are preferably 1-METHYLPYRROLIDONE (NMP), the viscosity of anode sizing agent and cathode size be preferably 1500～3000 Newton-seconds/square metre.
Step S3 is coated on anode sizing agent on the plus plate current-collecting body, and is then dry and roll film, cuts and is made into positive pole, and cathode size is coated on the negative current collector, then dry and roll film, cuts and is made into negative pole.Plus plate current-collecting body is preferably aluminium foil, and negative current collector is preferably Copper Foil.
Step S4, with described positive pole, barrier film and negative pole fit successively the assembling after be soaked in the electrolyte, obtain described super capacitance cell.In the present embodiment, with in parallel behind positive pole and negative pole and the membrane winding assembling rolling heart, weld behind the battery case of packing into, drying and dehydrating, injection electrolyte obtains the super capacitance cell of present embodiment after discharging and recharging activation.
The negative pole of above-mentioned super capacitance cell adopts the negative active core-shell material that consists of elemental silicon, silicon dioxide and Graphene, so that negative pole has low current potential platform, cause the average working voltage of super capacitance cell to be higher than traditional double electric layer capacitor, and silicon has characteristics capacious, the theoretical capacity 4200mAh/g of silicon, be far longer than the capacity 372mAh/g of graphite cathode, thereby the energy density of system is risen.The conductivity that grapheme material is good, grapheme material and elemental silicon and silicon dioxide is compound after, Graphene can well pass to electronics on the silicon materials, silicon materials are dispersed in and are conducive to the stable of material in the graphene sheet layer structure simultaneously.And in the silicon mixture that elemental silicon and silicon dioxide form, the existence of silicon dioxide can effectively slow down the capacity attenuation of elemental silicon, because it does not react silicon dioxide, also can slow down the capacity attenuation that elemental silicon causes because of volumetric expansion in charge and discharge process, thereby can be good at cushioning the expansion of elemental silicon in system, so that above-mentioned super capacitance cell has high-specific-power characteristic and high-energy-density characteristic concurrently.
Below be the specific embodiment part:
Embodiment 1
Anodal: as to be to mix at 85: 10: 5 in mass ratio with positive electrode active materials active carbon, binding agent PVDF and conductive agent acetylene black, add solvent NMP regulate slurry viscosity be 2500 Newton-seconds/square metre, through being coated on the aluminium foil, then dry and roll film, cut and be made into positive pole.
Negative pole: (1) is that 1: 10 SiO 2 powder mixes with the graphite oxide powder with mass ratio, ball milling is placed on that the speed with 10 ℃/minute slowly is warming up to 200 ℃ in the tube furnace of reducing atmosphere (percent by volume is the gaseous mixture that 5: 95 hydrogen and argon gas form), then Heat preservation is 1 hour, obtain mixture of powders, then in reducing atmosphere, cool to mixture of powders with the furnace room temperature, obtain consisting of the negative active core-shell material of silicon mixture and Graphene, wherein the mass ratio of silicon mixture and Graphene is 20: 80, and the mass ratio of elemental silicon and silicon dioxide is 1: 19 in the silicon mixture; The negative active core-shell material that (2) will consist of silicon mixture and Graphene and binding agent PVDF, conductive agent acetylene black are to mix at 85: 10: 5 in mass ratio, add solvent NMP regulate slurry viscosity be 2500 Newton-seconds/square metre, through being coated on the Copper Foil, then dry and roll film, cut and be made into negative pole.
Positive pole, barrier film and negative pole are stacked gradually rear employing winding method be assembled into the rouleau core, adopt the core parallel connection of 16 volumes pack into width, thickness and highly be respectively in the stainless steel battery case of 70mm, 34mm and 65mm.
With LiPF
6Be dissolved in the electrolyte that is prepared into 1mol/L in propene carbonate and the diethyl carbonate mixed liquor.
In a manner described the volume core of parallel connection is packed into and weld behind the battery case, drying and dehydrating injects electrolyte, obtains the super capacitance cell of present embodiment after discharging and recharging activation.
Fig. 2 is the constant current charge-discharge curve chart of the super capacitance cell of present embodiment, and wherein voltage range is 0～4 volt, and electric current is 1A/g, and equipment is the blue electric CT-2001A8 in the Wuhan battery test system of filling enamel.As shown in Figure 2, after tested, gained super capacitance cell average size is 4.2Ah, and energy density is 50wh/kg, and maximum power density is 5000W/kg.
Anodal: as to be that 70: 30 active carbon and LiFePO 4 material is mixed with positive electrode active materials with mass ratio.Be to mix at 90: 5: 5 in mass ratio with positive electrode active materials, binding agent PVDF and conductive agent acetylene black, add solvent NMP regulate slurry viscosity be 1500 Newton-seconds/square metre, then dry and roll film through being coated on the aluminium foil, cut and be made into positive pole.
Negative pole: (1) is that 1: 10 SiO 2 powder mixes with the graphite oxide powder with mass ratio, ball milling is placed on that the speed with 20 ℃/minute slowly is warming up to 400 ℃ in the tube furnace of reducing atmosphere (percent by volume is the gaseous mixture that 5: 95 hydrogen and argon gas form), then Heat preservation is 2 hours, obtain mixture of powders, then in reducing atmosphere, cool to mixture of powders with the furnace room temperature, obtain consisting of the negative active core-shell material of silicon mixture and Graphene, wherein the mass ratio of silicon mixture and Graphene is 20: 80, and the mass ratio of elemental silicon and silicon dioxide is 1: 3 in the silicon mixture; The negative active core-shell material that (2) will consist of silicon mixture and Graphene and binding agent PVDF and conductive agent acetylene black are to mix at 90: 5: 5 in mass ratio, add solvent NMP regulate slurry viscosity be 1500 Newton-seconds/square metre, through being coated on the Copper Foil, then dry and roll film, cut and be made into negative pole.
Positive pole, barrier film and negative pole are stacked gradually rear employing winding method be assembled into the rouleau core, adopt the core parallel connection of 16 volumes pack into width, thickness and highly be respectively in the stainless steel battery case of 70mm, 34mm and 65mm.
LiBOB is dissolved in the electrolyte that is prepared into 1mol/L in the acetonitrile solution.
In a manner described the volume core of parallel connection is packed into and weld behind the battery case, drying and dehydrating injects electrolyte, obtains the super capacitance cell of present embodiment after discharging and recharging activation.
After tested, gained super capacitance cell average size is 4.5Ah, and energy density is 60wh/kg, and maximum power density is 4000W/kg.
Anodal: the carbon aerogels that with mass ratio is 80: 20 becomes positive electrode active materials with the lithium nickel cobalt manganese oxygen material formulation.Be 85: 10: 5 mixed preparing form slurry in mass ratio with positive electrode active materials, binding agent PVDF and conductive agent conductive black supperP, add solvent NMP regulate slurry viscosity be 3000 Newton-seconds/square metre, through being coated on the aluminium foil, then dry and roll film, cut and be made into positive pole.
Negative pole: (1) is that 1: 10 SiO 2 powder mixes with the graphite oxide powder with mass ratio, ball milling is placed on that the speed with 50 ℃/minute slowly is warming up to 600 ℃ in the tube furnace of reducing atmosphere (percent by volume is the gaseous mixture that 5: 95 hydrogen and argon gas form), then Heat preservation is 5 hours, obtain mixture of powders, then in reducing atmosphere, cool to mixture of powders with the furnace room temperature, obtain consisting of the negative active core-shell material of silicon mixture and Graphene, wherein the mass ratio of silicon mixture and Graphene is 20: 80, and the mass ratio of elemental silicon and silicon dioxide is 1: 1 in the silicon mixture; The negative active core-shell material that (2) will consist of silicon mixture and Graphene and binding agent PVDF and conductive agent conductive black supperP mix at 85: 10: 5, add solvent NMP regulate slurry viscosity be 3000 Newton-seconds/square metre, through being coated on the Copper Foil, then dry and roll film, cut and be made into negative pole.
Positive pole, barrier film and negative pole are stacked gradually rear employing winding method be assembled into the rouleau core, adopt the core parallel connection of 16 volumes pack into width, thickness and highly be respectively in the stainless steel battery case of 70mm, 34mm and 65mm.
With LiBF
4Be dissolved in the electrolyte that is prepared into 1mol/L in dimethyl carbonate and the ethylene carbonate mixed liquor.
In a manner described the volume core of parallel connection is packed into and weld behind the battery case, drying and dehydrating injects electrolyte, obtains the super capacitance cell of present embodiment after discharging and recharging activation.
After tested, gained super capacitance cell average size is 4.7Ah, and energy density is 60wh/kg, and maximum power density is 5000W/kg.
Embodiment 4
Anodal: the carbon nano-tube that with mass ratio is 90: 10 becomes positive electrode active materials with lithium manganese oxygen material formulation.Be to mix at 90: 5: 5 in mass ratio with positive electrode active materials, binding agent PVDF and conductive agent carbon nano-tube, add solvent NMP regulate slurry viscosity be 2000 Newton-seconds/square metre, through being coated on the aluminium foil, do then dryly and roll film, cut and be made into positive pole.
Negative pole: (1) is that 1: 10 SiO 2 powder mixes with the graphite oxide powder with mass ratio, the tube furnace of putting into reducing atmosphere (percent by volume is 5: 95 hydrogen and the composition gaseous mixture of argon gas) behind the ball milling slowly is warming up to 800 ℃ with 80 ℃/minute speed, then Heat preservation is 10 hours, obtain mixture of powders, then in reducing atmosphere, cool to mixture of powders with the furnace room temperature, obtain consisting of the negative active core-shell material of silicon mixture and Graphene, wherein the mass ratio of silicon mixture and Graphene is 20: 80, and the mass ratio of elemental silicon and silicon dioxide is 18: 2 in the silicon mixture; The negative active core-shell material that (2) will consist of silicon and Graphene and binding agent PVDF and conductive agent carbon nano-tube are to mix at 90: 5: 5 in mass ratio, add solvent NMP regulate slurry viscosity be 2000 Newton-seconds/square metre, through being coated on the Copper Foil, then dry and roll film, cut and be made into negative pole.
Positive pole, barrier film and negative pole are stacked gradually rear employing winding method be assembled into the rouleau core, adopt the core parallel connection of 16 volumes pack into width, thickness and highly be respectively in the stainless steel battery case of 70mm, 34mm and 65mm.
With LiBF
4Be dissolved in the electrolyte that is prepared into 1mol/L in propene carbonate and the diethyl carbonate mixed liquor.
In a manner described the volume core of parallel connection is packed into and weld behind the battery case, drying and dehydrating injects electrolyte, obtains the super capacitance cell of present embodiment after discharging and recharging activation.
After tested, gained super capacitance cell average size is 5.2Ah, and energy density is 66wh/kg, and maximum power density is 6000W/kg.
Embodiment 5
Anodal: the pyrolytic carbon that with mass ratio is 85: 15 becomes positive electrode active materials with lithium cobalt oxygen material formulation.Be to mix at 85: 10: 5 in mass ratio with positive electrode active materials, binding agent PVDF and conductive agent acetylene black, add solvent NMP regulate slurry viscosity be 2700 Newton-seconds/square metre, then dry and roll film through being coated on the aluminium foil, cut and be made into positive pole.
Negative pole: (1) will mix, ball milling is placed on that the speed with 100 ℃/minute slowly is warming up to 1200 ℃ in the tube furnace of reducing atmosphere (percent by volume is the gaseous mixture that 5: 95 hydrogen and argon gas form), then Heat preservation is 8 hours, obtain mixture of powders, then in reducing atmosphere, cool to mixture of powders with the furnace room temperature, obtain consisting of the negative active core-shell material of silicon mixture and Graphene, wherein the mass ratio of silicon mixture and Graphene is 20: 80, elemental silicon and the mass ratio of silicon dioxide be 19: 1 (2) negative active core-shell material that will consist of silicon mixture and Graphene with binding agent PVDF and conductive agent acetylene black are to mix at 85: 10: 5 in mass ratio in the silicon mixture, add solvent NMP regulate slurry viscosity be 2700 Newton-seconds/square metre, through being coated on the Copper Foil, then dry and roll film, cut and be made into negative pole.
Positive pole, barrier film and negative pole are stacked gradually rear employing winding method be assembled into the rouleau core, adopt the core parallel connection of 16 volumes pack into width, thickness and highly be respectively in the stainless steel battery case of 70mm, 34mm and 65mm.
With LiCF
3SO
3Be dissolved in the electrolyte that is prepared into 1mol/L in the acetonitrile solution.
In a manner described the volume core of parallel connection is packed into and weld behind the battery case, drying and dehydrating injects electrolyte, obtains the super capacitance cell of present embodiment after discharging and recharging activation.
After tested, gained super capacitance cell average size is 5.3Ah, and energy density is 68wh/kg, and maximum power density is 5800W/kg.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. super capacitance cell, comprise positive pole, negative pole, the barrier film between described positive pole and negative pole and electrolyte, described positive pole, negative pole and barrier film are soaked in the described electrolyte, it is characterized in that, described positive pole comprises plus plate current-collecting body and is coated on positive electrode on the described plus plate current-collecting body, described positive electrode comprises positive electrode active materials, the first binding agent and the first conductive agent, described positive electrode active materials is comprised of carbon materials and lithium ion material, and the content of carbon materials is more than or equal to 70% and less than 100% described in the described positive electrode active materials; Described negative pole comprises negative current collector and is coated on negative material on the described negative current collector, described negative material comprises negative active core-shell material, the second binding agent and the second conductive agent, described negative active core-shell material is comprised of silicon mixture and Graphene, the mass ratio of described silicon mixture and Graphene is 1～20: 80～99, described silicon mixture is comprised of elemental silicon and silicon dioxide, and the mass ratio of described elemental silicon and silicon dioxide is 1: 19～19: 1.
2. super capacitance cell according to claim 1 is characterized in that, the mass ratio of described positive electrode active materials, the first binding agent and the first conductive agent is 85～90: 5～10: 5～10; The mass ratio of described negative active core-shell material, the second binding agent and the second conductive agent is 85～90: 5～10: 5～10.
3. super capacitance cell according to claim 1 is characterized in that, described lithium ion material is LiFePO4, lithium nickel cobalt manganese oxygen, lithium cobalt oxygen, lithium manganese oxygen, Li-Ni-Mn-O, lithium-nickel-cobalt-oxygen, lithium vanadium oxygen or ferric metasilicate lithium.
4. super capacitance cell according to claim 1 is characterized in that, described the first conductive agent and the second conductive agent are acetylene black, conductive black or carbon nano-tube; Described the first binding agent and the second binding agent are Kynoar.
5. the preparation method of a super capacitance cell is characterized in that, comprises the steps:
Step 1: carbon materials is mixed with into positive electrode active materials with the lithium ion material, the content of carbon materials is more than or equal to 70% and less than 100% described in the described positive electrode active materials, be that 1～20: 80～99 silicon mixture is mixed with into negative active core-shell material with Graphene with mass ratio, described silicon mixture is that 1: 19～19: 1 elemental silicon and silicon dioxide forms by mass ratio;
Step 2: described positive electrode active materials and the first binding agent, the first conductive agent and the first solvent are mixed with anode sizing agent, described negative active core-shell material and the second binding agent, the second conductive agent and the second solvent are mixed with cathode size;
Step 3: described anode sizing agent is coated on the plus plate current-collecting body, then dry, roll film, cut and be made into positive pole, described cathode size is coated on the negative current collector, then dry, roll film, cut and be made into negative pole; And
Step 4: with described positive pole, barrier film and negative pole fit successively the assembling after be soaked in the electrolyte, obtain described super capacitance cell.
6. the preparation method of super capacitance cell according to claim 5, it is characterized in that, in the step 1, the preparation process of described negative active core-shell material also comprises the steps: SiO 2 powder and graphite oxide powder are mixed with mixture, described mixture ball milling is placed on the speed with 10～100 ℃/minute is warming up to 200～1200 ℃ under the reducing atmosphere, heat and obtained mixture of powders in 1～10 hour, then described mixture of powders is cooled to room temperature in reducing atmosphere, obtains described negative active core-shell material.
7. the preparation method of super capacitance cell according to claim 5 is characterized in that, in the step 2, the mass ratio of described positive electrode active materials, the first binding agent and the first conductive agent is 85～90: 5～10: 5～10; The mass ratio of described negative active core-shell material, the second binding agent and the second conductive agent is 85～90: 5～10: 5～10.
8. the preparation method of super capacitance cell according to claim 5 is characterized in that, in the step 2, described the first solvent and the second solvent are 1-METHYLPYRROLIDONE, the viscosity of described anode sizing agent and cathode size be 1500～3000 Newton-seconds/square metre.
9. the preparation method of super capacitance cell according to claim 5 is characterized in that, in the step 3, described plus plate current-collecting body is aluminium foil, and described negative current collector is Copper Foil.
10. the preparation method of super capacitance cell according to claim 5 is characterized in that, in the step 4, described electrolyte is that lithium-ion electrolyte salt and non-aqueous organic solvent are formulated.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070516A (en) * | 2015-09-08 | 2015-11-18 | 上海空间电源研究所 | High-specific-energy super capacitor positive pole sheet and preparation method thereof |
| CN105513814A (en) * | 2015-12-15 | 2016-04-20 | 宁波南车新能源科技有限公司 | Energy type capacitor battery |
| CN105990603A (en) * | 2016-07-04 | 2016-10-05 | 吴杨 | High-power super-capacitor lithium battery and preparation method thereof |
| CN106098409A (en) * | 2016-07-31 | 2016-11-09 | 肖丽芳 | A kind of preparation method containing lithium ion conducting polymer coating positive plate |
| CN108987129A (en) * | 2018-07-06 | 2018-12-11 | 凌容新能源科技（上海）股份有限公司 | The application of high energy battery capacitor fabrication method and high energy battery capacitor |
| CN109659141A (en) * | 2018-11-06 | 2019-04-19 | 东莞新发电子有限公司 | Composite battery capacitor and preparation method thereof |
| CN110085840A (en) * | 2019-05-05 | 2019-08-02 | 南通沃德材料科技有限公司 | A kind of lead carbon battery conduction negative electrode material and its manufacture craft |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101079510A (en) * | 2007-06-25 | 2007-11-28 | 中南大学 | A super capacitance cell |
| CN101924211A (en) * | 2010-08-19 | 2010-12-22 | 北京科技大学 | Graphene/silicon lithium ion battery cathode material and preparation method thereof |
| CN101699590B (en) * | 2009-11-03 | 2011-08-31 | 朝阳立塬新能源有限公司 | Hybrid supercapacitor |
-
2011
- 2011-09-15 CN CN2011102737540A patent/CN103000383A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101079510A (en) * | 2007-06-25 | 2007-11-28 | 中南大学 | A super capacitance cell |
| CN101699590B (en) * | 2009-11-03 | 2011-08-31 | 朝阳立塬新能源有限公司 | Hybrid supercapacitor |
| CN101924211A (en) * | 2010-08-19 | 2010-12-22 | 北京科技大学 | Graphene/silicon lithium ion battery cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LIWEI SU,ET AL: "Core double-shell Si@SiO2@C nanocomposites as anode materials for Li-ion batteries", 《CHEMICAL COMMUNICATION》, vol. 46, no. 15, 5 February 2010 (2010-02-05), XP002728259, DOI: doi:10.1039/B925696B * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070516A (en) * | 2015-09-08 | 2015-11-18 | 上海空间电源研究所 | High-specific-energy super capacitor positive pole sheet and preparation method thereof |
| CN105513814A (en) * | 2015-12-15 | 2016-04-20 | 宁波南车新能源科技有限公司 | Energy type capacitor battery |
| CN105990603A (en) * | 2016-07-04 | 2016-10-05 | 吴杨 | High-power super-capacitor lithium battery and preparation method thereof |
| CN106098409A (en) * | 2016-07-31 | 2016-11-09 | 肖丽芳 | A kind of preparation method containing lithium ion conducting polymer coating positive plate |
| CN108987129A (en) * | 2018-07-06 | 2018-12-11 | 凌容新能源科技（上海）股份有限公司 | The application of high energy battery capacitor fabrication method and high energy battery capacitor |
| CN109659141A (en) * | 2018-11-06 | 2019-04-19 | 东莞新发电子有限公司 | Composite battery capacitor and preparation method thereof |
| CN110085840A (en) * | 2019-05-05 | 2019-08-02 | 南通沃德材料科技有限公司 | A kind of lead carbon battery conduction negative electrode material and its manufacture craft |
| CN110085840B (en) * | 2019-05-05 | 2022-03-04 | 卢云峰 | Lead-carbon battery conductive negative electrode material and manufacturing process thereof |
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Application publication date: 20130327 |