CN103065799A - Super-capacitor battery and preparation method thereof - Google Patents
Super-capacitor battery and preparation method thereof Download PDFInfo
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- 239000010703 silicon Substances 0.000 claims abstract description 56
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000006230 acetylene black Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000005030 aluminium foil Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical compound [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004964 aerogel Substances 0.000 claims description 4
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 claims description 4
- CPABIEPZXNOLSD-UHFFFAOYSA-N lithium;oxomanganese Chemical compound [Li].[Mn]=O CPABIEPZXNOLSD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
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- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- UXOBGPZQFFWWHD-UHFFFAOYSA-N lithium;oxovanadium Chemical compound [Li].[V]=O UXOBGPZQFFWWHD-UHFFFAOYSA-N 0.000 claims description 3
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 description 3
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 3
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- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 1
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Abstract
A super-capacitor battery comprises a positive electrode, a negative electrode, a separating membrane between the positive electrode and the negative electrode, and electrolyte solution. The positive electrode, the negative electrode and the separating membrane are steeped in the electrolyte solution. The negative electrode comprises a negative electrode current collector and negative electrode materials coated on the negative electrode current collector. The negative materials comprise negative electrode active materials, second binder and second conductive agent. The negative active materials are composed of silicon nanowires, carbon nano tubes and grapheme. The mass ratio of the silicon nanowires, the carbon nano tubes and the grapheme is 1:0.5-5:(0.5-5). Due to the fact that the negative electrode of the super-capacitor battery is composed of the silicon nanowires, the carbon nano tubes and the grapheme, the negative electrode is provided with a low electric potential platform, the average working voltage of the super-capacitor battery is increased, and therefore the super-capacitor battery is enabled to have a height-ratio power characteristic and a high-ratio energy characteristic. In addition, the invention further provides a preparation method of the super-capacitor 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 super capacitance cell 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 by carbon materials or by the compositions of mixtures of carbon materials and lithium ion material, the content of carbon materials is more than or equal to 70% and less than 100% described in the described mixture; 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 nanowires, carbon nano-tube and Graphene, and the mass ratio of described silicon nanowires, carbon nano-tube and Graphene is 1: 0.5～5: 0.5～5.
In a preferred embodiment, the length of described silicon nanowires is 10nm～1 μ m, and diameter is 1nm～100nm; The length of described carbon nano-tube is 10nm～1 μ m, and diameter is 1nm～100nm; The specific surface of described Graphene is 200m
2/ g～600m
2/ g.
In a preferred embodiment, described carbon materials is active carbon, charcoal-aero gel, carbon nano-tube or RESEARCH OF PYROCARBON; 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.
A kind of preparation method of super capacitance cell comprises the steps:
Step 1: carbon materials or the mixture that is comprised of carbon materials and lithium ion material are mixed with positive electrode active materials, and the content of carbon materials is more than or equal to 70% and less than 100% described in the described mixture; Be 1: 0.5～5: 0.5～5 to be prepared into negative active core-shell material in mass ratio with silicon nanowires, carbon nano-tube and Graphene;
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 and roll film, cut and be made into positive pole, described cathode size is coated on the negative current collector, then dry and 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, the preparation process of described negative active core-shell material also comprises the steps: silicon nanowires, carbon nano-tube are mixed with Graphene, and ball milling 0.5～5 hour obtains described negative active core-shell material.
In a preferred embodiment, in the step 1, the length of described silicon nanowires is 10nm～1 μ m, and diameter is 1nm～100nm; The length of described carbon nano-tube is 10nm～1 μ m, and diameter is 1nm～100nm; The specific surface of described Graphene is 200m
2/ g～600m
2/ g.
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 silicon nanowires, carbon nano-tube 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.Grapheme material and carbon nano-tube, silicon nanowires carry out compound after, because the good conductivity of grapheme material, can well electronics be passed on the silicon nanowires, the carbon nano-tube of the silicon nanowires of one dimension and one dimension is intertwined and forms three-dimensional network to be conducive to the stable of material, so that above-mentioned super capacitance cell has high-specific-power characteristic and high-energy-density characteristic concurrently simultaneously.
[description of drawings]
Fig. 1 is the super capacitance cell preparation method flow chart of an execution mode;
Fig. 2 is the scanning electron microscope (SEM) photograph of silicon nanowires-carbon nano-tube-graphene composite material of embodiment 1;
Fig. 3 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 capacitance cell 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, and 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.
Positive electrode active materials is by carbon materials or by the compositions of mixtures of carbon materials and lithium ion material.In the described mixture, the content of carbon materials is more than or equal to 70% and less than 100%.Carbon materials is preferably active carbon, charcoal-aero gel, carbon nano-tube or pyrolytic carbon.The lithium ion material is preferably 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.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 comprised of silicon nanowires, carbon nano-tube and Graphene.The mass ratio of silicon nanowires, carbon nano-tube and Graphene is 1: 0.5～5: 0.5～5.Wherein, the length of silicon nanowires is preferably 10nm～1 μ m, and diameter is 1nm～100nm; The length of carbon nano-tube is preferably 10nm～1 μ m, and diameter is 1nm～100nm; The specific surface of Graphene is preferably 200m
2/ g～600m
2/ g.Grapheme material and silicon nanowires, carbon nano-tube are advanced the compound negative pole that is prepared into, so that negative pole has than the electronegative potential platform, increased the average working voltage of super capacitance cell, and the carbon nano-tube of the silicon nanowires of one dimension and the one dimension formation three-dimensional network that is intertwined, be conducive to the stable of material.
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 the common conductive agent such as acetylene black, conductive black 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 LiPF
6, LiBF
4, LiBOB, LiCF
3SO
3, LiN (SO
2CF
3)
2Or 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.
Grapheme material not only possesses good conductivity, and the space distributes and high mechanical performance, possess simultaneously low cost, and technique is simple, is easy to preparation, and the electrode material for preparing has good electrochemical stability.
The one-dimensional nano structure of silicon is considered to be expected to become the basis of following microelectronics and opto-electronic device, one dimension nano silicon material can be relatively easy to compatible mutually with the integrated circuit technology of current maturation, can bringing into play its unique performance aspect the nanometer confinement effect, reach excellent properties that some materials are beyond one's reach again.
As shown in Figure 1, the preparation method of above-mentioned super capacitance cell comprises the steps:
Step S1 is mixed with positive electrode active materials with carbon materials or the mixture that 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 mixture; Be 1: 0.5～5: 0.5～5 to be prepared into negative active core-shell material in mass ratio with silicon nanowires, carbon nano-tube and Graphene.In the present embodiment, the preparation process of negative active core-shell material also comprises the steps: in mass ratio silicon nanowires, carbon nano-tube to be mixed with Graphene, and ball milling 0.5～5 hour obtains negative active core-shell material.In a preferred embodiment, adopt chemical gaseous phase deposition method (selecting from Journal of Power Sources 195 (2010) 1691-1697) preparation silicon nanowires, be appreciated that silicon nanowires also can adopt the preparation methods such as thermal evaporation, solwution method or electrochemical process to obtain.The length of silicon nanowires is preferably 10nm～1 μ m, and diameter is 1nm～100nm.The length of carbon nano-tube is preferably 10nm～1 μ m, and diameter is 1nm～100nm; The specific surface of Graphene is preferably 200m
2/ g～600m
2/ g.Carbon nano-tube and Graphene all can obtain by conventional method.
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 described 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 positive pole, barrier film and negative pole fit successively the assembling after be soaked in the electrolyte, obtain 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 silicon nanowires 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.Grapheme material and silicon nanowires carry out compound after, because the good conductivity of grapheme material, can well electronics be passed on the silicon nanowires, the carbon nano-tube of the silicon nanowires of one dimension and one dimension is intertwined and forms three-dimensional network to be conducive to the stable of material, so that above-mentioned super capacitance cell has high-specific-power characteristic and high-energy-density characteristic concurrently simultaneously.
Below be the specific embodiment part:
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 drying and roll film is cut and is made into positive pole.
Negative pole: (1) is by the standby silicon nanowires that obtains of CVD legal system; (2) silicon nanowires, carbon nano-tube mixed with Graphene in 1: 0.5: 0.5 in mass ratio, ball milling 1 hour obtains negative active core-shell material; Wherein, the length of silicon nanowires is 10nm, and diameter is 1nm; The length of carbon nano-tube is 10nm, and diameter is 1nm; The specific surface of Graphene is 200m
2/ g; (3) be to mix at 85: 10: 5 in mass ratio with negative active core-shell material and binding agent PVDF and conductive agent acetylene black, add solvent NMP regulate slurry viscosity be 2500 Newton-seconds/square metre, then dry and roll film through being coated on the Copper Foil, 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.
See also Fig. 2, be depicted as the scanning electron microscope (SEM) photograph of silicon nanowires-carbon nano-tube-graphene composite material.As shown in Figure 2, the silicon nanowires of one dimension mutually twines with the carbon nano-tube of one dimension and forms the three-dimensional network material with Graphene.
Fig. 3 is the constant current charge-discharge curve chart of the super capacitance cell of the 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 3, after tested, gained super capacitance cell average size is 5Ah, and energy density is 70wh/kg, and maximum power density is 6000W/kg.
Anodal: as to be that 70: 30 charcoal-aero gel 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 the positive electrode active materials for preparing and 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 by the standby silicon nanowires that obtains of CVD legal system; (2) silicon nanowires, carbon nano-tube mixed with Graphene in 1: 5: 5 in mass ratio, ball milling 0.5 hour obtains negative active core-shell material; Wherein, the length of silicon nanowires is preferably 50nm, and diameter is 10nm; The length of carbon nano-tube is preferably 50 μ m, and diameter is 10nm; The specific surface of Graphene is preferably 300m
2/ g; (3) be to mix at 90: 5: 5 in mass ratio with negative active core-shell material and 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 Copper Foil, 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 65wh/kg, and maximum power density is 6000W/kg.
Anodal: the carbon nano-tube that with mass ratio is 80: 20 becomes positive electrode active materials with the lithium nickel cobalt manganese oxygen material formulation.Be to mix at 85: 10: 5 in mass ratio with the positive electrode active materials for preparing and binding agent PVDF and conductive agent conductive black, 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 by the standby silicon nanowires that obtains of CVD legal system; (2) silicon nanowires, carbon nano-tube mixed with Graphene in 1: 2.5: 2.5 in mass ratio, ball milling 2 hours obtains negative active core-shell material; Wherein, the length of silicon nanowires is preferably 100nm, and diameter is 50nm; The length of carbon nano-tube is preferably 100nm, and diameter is 50nm; The specific surface of Graphene is preferably 400m
2/ g; (3) be to mix at 85: 10: 5 in mass ratio with negative active core-shell material and binding agent PVDF and conductive agent conductive black, 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 4Ah, and energy density is 60wh/kg, and maximum power density is 7000W/kg.
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 the positive electrode active materials for preparing and 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, then dry and roll film, cut and be made into positive pole.
Negative pole: (1) is by the standby silicon nanowires that obtains of CVD legal system; (2) silicon nanowires, carbon nano-tube mixed with Graphene in 1: 2: 3 in mass ratio, ball milling 5 hours obtains negative active core-shell material; Wherein, the length of silicon nanowires is preferably 500nm, and diameter is 80nm; The length of carbon nano-tube is preferably 500nm, and diameter is 80nm; The specific surface of Graphene is preferably 500m
2/ g; (3) be to mix at 90: 5: 5 in mass ratio with negative active core-shell material and 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 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 capacity is 4.2Ah, and energy density is 63wh/kg, and maximum power density is 6500W/kg.
Anodal: the pyrolytic carbon that with mass ratio is 15: 85 becomes positive electrode active materials with lithium cobalt oxygen material formulation.Be to mix at 85: 10: 5 in mass ratio with the positive electrode active materials for preparing and binding agent PVDF and conductive agent acetylene black, add solvent NMP regulate slurry viscosity be 2700 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 by the standby silicon nanowires that obtains of CVD legal system; (2) silicon nanowires, carbon nano-tube mixed with Graphene in 1: 4: 2 in mass ratio, ball milling 3 hours obtains negative active core-shell material; Wherein, the length of silicon nanowires is preferably 1 μ m, and diameter is 100nm; The length of carbon nano-tube is preferably 1 μ m, and diameter is 100nm; The specific surface of Graphene is preferably 600m
2/ g; (3) be to mix at 85: 10: 5 in mass ratio with negative active core-shell material and 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 Copper Foil, 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 4.8Ah, and energy density is 68wh/kg, and maximum power density is 7000W/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, 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 by carbon materials or by the compositions of mixtures of carbon materials and lithium ion material, the content of carbon materials is more than or equal to 70% and less than 100% described in the described mixture; 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 nanowires, carbon nano-tube and Graphene, and the mass ratio of described silicon nanowires, carbon nano-tube and Graphene is 1: 0.5～5: 0.5～5.
2. super capacitance cell according to claim 1 is characterized in that, the length of described silicon nanowires is 10nm～1 μ m, and diameter is 1nm～100nm; The length of described carbon nano-tube is 10nm～1 μ m, and diameter is 1nm～100nm; The specific surface of described Graphene is 200m
2/ g～600m
2/ g.
3. super capacitance cell according to claim 1 is characterized in that, described carbon materials is active carbon, charcoal-aero gel, carbon nano-tube or RESEARCH OF PYROCARBON; 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 or the mixture that is comprised of carbon materials and lithium ion material are mixed with positive electrode active materials, and the content of carbon materials is more than or equal to 70% and less than 100% described in the described mixture; Be 1: 0.5～5: 0.5～5 to be prepared into negative active core-shell material in mass ratio with silicon nanowires, carbon nano-tube and Graphene;
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 and roll film, cut and be made into positive pole, described cathode size is coated on the negative current collector, then dry and 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, the preparation process of described negative active core-shell material also comprises the steps: silicon nanowires, carbon nano-tube are mixed with Graphene, and ball milling 0.5～5 hour 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 1, the length of described silicon nanowires is 10nm～1 μ m, and diameter is 1nm～100nm; The length of described carbon nano-tube is 10nm～1 μ m, and diameter is 1nm～100nm; The specific surface of described Graphene is 200m
2/ g～600m
2/ g.
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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| CN105576203A (en) * | 2015-12-23 | 2016-05-11 | 厦门大学 | Graphene/silicone/carbon nano tube composite material and preparation method and application thereof |
| CN105789608A (en) * | 2016-03-29 | 2016-07-20 | 华南师范大学 | A kind of preparation method and application of Si/MnO2/graphene/carbon lithium ion battery negative electrode material |
| CN107248451A (en) * | 2017-07-28 | 2017-10-13 | 中国科学院电工研究所 | A kind of lithium-ion capacitor of high-energy-density |
| CN115616054A (en) * | 2022-10-29 | 2023-01-17 | 福州大学 | A kind of preparation method of silicon-based composite photoelectrode |
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| CN101079510A (en) * | 2007-06-25 | 2007-11-28 | 中南大学 | A super capacitance cell |
| CN102214817A (en) * | 2010-04-09 | 2011-10-12 | 清华大学 | Carbon/silicon/carbon nano composite structure cathode material and preparation method thereof |
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| CN101079510A (en) * | 2007-06-25 | 2007-11-28 | 中南大学 | A super capacitance cell |
| CN102214817A (en) * | 2010-04-09 | 2011-10-12 | 清华大学 | Carbon/silicon/carbon nano composite structure cathode material and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105406044A (en) * | 2015-12-16 | 2016-03-16 | 上海航天电源技术有限责任公司 | Expansion-resistant silicon-carbon negative electrode plate and preparation method therefor |
| CN105406044B (en) * | 2015-12-16 | 2019-04-12 | 上海航天电源技术有限责任公司 | A kind of silicon-carbon cathode piece of anti-expansion and preparation method thereof |
| CN105576203A (en) * | 2015-12-23 | 2016-05-11 | 厦门大学 | Graphene/silicone/carbon nano tube composite material and preparation method and application thereof |
| CN105789608A (en) * | 2016-03-29 | 2016-07-20 | 华南师范大学 | A kind of preparation method and application of Si/MnO2/graphene/carbon lithium ion battery negative electrode material |
| CN105789608B (en) * | 2016-03-29 | 2019-02-05 | 华南师范大学 | A kind of preparation method and application of negative electrode material of Si/MnO2/graphene/carbon lithium ion battery |
| CN107248451A (en) * | 2017-07-28 | 2017-10-13 | 中国科学院电工研究所 | A kind of lithium-ion capacitor of high-energy-density |
| CN107248451B (en) * | 2017-07-28 | 2019-01-11 | 中国科学院电工研究所 | A kind of lithium-ion capacitor of high-energy density |
| CN115616054A (en) * | 2022-10-29 | 2023-01-17 | 福州大学 | A kind of preparation method of silicon-based composite photoelectrode |
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Application publication date: 20130424 |