CN105655147A - Lithium-ion capacitor negative electrode unit and preparation method thereof, and lithium-ion capacitor - Google Patents
Lithium-ion capacitor negative electrode unit and preparation method thereof, and lithium-ion capacitor Download PDFInfo
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- CN105655147A CN105655147A CN201610037631.XA CN201610037631A CN105655147A CN 105655147 A CN105655147 A CN 105655147A CN 201610037631 A CN201610037631 A CN 201610037631A CN 105655147 A CN105655147 A CN 105655147A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention relates to a lithium-ion capacitor negative electrode unit and a preparation method thereof, and a lithium-ion capacitor, and belongs to the technical field of the lithium-ion capacitors. The lithium-ion capacitor negative electrode unit comprises a negative electrode sheet. The negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer coated on the surface of the negative electrode current collector. A lithium net is arranged on the surface of the negative electrode active material layer. According to the invention, the lithium net is arranged on the surface of the negative electrode sheet, an electrolyte is enabled to infiltrate the lithium net rapidly, the lithium net is in sufficient contact with the electrolyte, and the sufficient lithium embedding of the negative electrode sheet is ensured; in addition, an "escape" channel is provided for gas produced from the surface of the negative electrode sheet, the gas is discharged in time, the separation of the lithium net from the negative electrode sheet, due to the gathering of gas on the surface of the negative electrode sheet, is avoided, the falling of the negative electrode active material is also avoided, and the self-discharging probability is lowered.
Description
Technical field
The present invention relates to a kind of lithium-ion capacitor negative pole unit and preparation method thereof, lithium-ion capacitor, belong to lithium-ion capacitor technical field.
Background technology
Along with deepening continuously of utilization of energy, various energy storage devices such as lead-acid battery, Ni-MH battery, lithium ion battery etc. all get a larger development. Along with developing rapidly of electric motor car market in recent years, the energy density of energy storage device and the requirement of power density is also more and more higher, the energy density of traditional secondary cell is higher, but power density is low, the electric vehicle power requirement to electrical source of power cannot be met, and the energy density of traditional capacitor is relatively low, also cannot meet the electric vehicle requirement to electrical source of power energy density, in this case, lithium-ion capacitor become a kind of can the effective solution of balanced above-mentioned requirements.
Lithium-ion capacitor have employed the principle design of double layer capacitor, but the positive electrode of textural employing lithium ion battery negative material and double layer capacitor combines, substantially increase the energy density of capacitor, also having very high power density and cycle life, performance is better than traditional lithium ion battery and double layer capacitor simultaneously.
Lithium-ion capacitor carbonaceous negative pole need to carry out pre-embedding lithium so that it is current potential step-down and smooth, and can improve the energy density of capacitor. Japanese fuji heavy industry Co., Ltd. discloses the manufacturing technology of a kind of lithium-ion capacitor, this technology introduces the 3rd pole " lithium electrode ", the independent outside being placed on lithium-ion capacitor or inside, both positive and negative polarity collector have employed the aluminium foil and Copper Foil with through hole characteristic; When injecting electrolyte, lithium electrode just starts to discharge lithium ion and carry out embedding lithium to negative pole, it is relatively uniform that this structure can realize embedding lithium, but owing to both positive and negative polarity collector have employed the aluminium foil and Copper Foil with through hole characteristic, not only complex manufacturing technology, production cost is higher, and electric conductivity is poor, and the difference of the carrying lithium amount of every layer of cathode pole piece is also bigger.
Authorization Notice No. is that CN204360933U (authorized announcement date is on May 27th, 2015) discloses a kind of super lithium-ion capacitor, including positive pole, negative pole, barrier film and electrolyte, positive pole includes the first collector and is arranged at the active carbon layer of the first collection liquid surface, described negative pole includes the second collector and is arranged at the hard carbon layer of described second collection liquid surface, described barrier film is arranged between described positive pole and described negative pole, so that described positive pole and the insulation of described negative electricity, described electrolyte and described positive pole and negative pole physical contact and electrical contact, to allow ion to exchange between described positive pole and described negative pole, described super lithium-ion capacitor also includes lithium lamella, described lithium lamella is between described hard carbon layer and described barrier film and is arranged on described hard carbon layer surface.After lithium-ion capacitor fluid injection, lithium lamella can mend lithium to negative pole, makes negative plate have lithium deposit comparatively fully, improves the energy density of lithium-ion capacitor to a certain extent. But in this technical scheme, lithium lamella is insufficient with electrolyte contacts, it is impossible to making lithium and negative pole fully react efficiently, in improving the energy density of lithium-ion capacitor, effect is very limited, and also results in the waste of lithium lamella. Additionally, lithium-ion capacitor is the same with lithium ion battery, gas can be produced due to the formation of SEI film when Lithium-ion embeding negative pole, in such scheme, lithium lamella covers the hard carbon layer surface of negative plate, affects the timely discharge of gas, when gas between negative plate and lithium sheet gathers more, contacting of lithium sheet and negative plate surface can be hindered, cause that lithium sheet departs from from negative plate surface and come, cause the failure of pre-embedding lithium; The serious negative electrode active material that results even in departs from from collection liquid surface, forms conductive particle in the capacitor, causes that capacitor self discharge probability increases.
Summary of the invention
It is an object of the invention to provide a kind of lithium-ion capacitor negative pole unit, the problem that the negative plate By Electrolysis liquid to solve lithium-ion capacitor of the prior art cannot be fully contacted and the gas on negative plate surface cannot be discharged in time with lithium sheet. The present invention also aims to the preparation method of a kind of above-mentioned lithium-ion capacitor negative pole unit is provided and uses the lithium-ion capacitor of above-mentioned lithium-ion capacitor negative pole unit.
In order to realize object above, the technical scheme of the lithium-ion capacitor negative pole unit of the present invention is as follows:
A kind of lithium-ion capacitor negative pole unit, including negative plate, described negative plate includes negative current collector and is coated in the negative electrode active material layer of negative pole currect collecting surface, and described negative electrode active material layer surface is equipped with lithium net.
The lithium-ion capacitor negative pole unit of the present invention adopts at negative plate surface configuration lithium net, by lithium net to the embedding lithium of negative plate, electrolyte and lithium net can be made quickly to infiltrate, lithium net and electrolyte are fully contacted, it is ensured that the abundant embedding lithium of negative plate, can provide " escape " passage for the gas that negative plate surface produces again, gas is made to discharge in time, avoid gas to gather the lithium net caused on negative plate surface to depart from negative plate, it also avoid coming off of negative electrode active material, reduce self discharge probability. The lithium net on the negative plate surface of the present invention can also make most lithium all realize contacting with negative plate, fully there is electrochemical reaction, improve the utilization rate of lithium, it is easy to control cost, also allow for making by controlling the porosity of lithium net when mending lithium demand and being certain the negative electrode active material layer on lithium net complete uniform fold negative plate surface, make embedding lithium more uniform. The present invention can effectively control the lithium load capacity of each layer of cathode pole piece, and owing to being required for the Copper Foil with through hole characteristic, can reduce cost, can also reduce internal resistance simultaneously, improve the electric conductivity of collector.
The quality of described lithium net is compared with the quality of negative electrode active material, unsuitable too much, to avoid causing cost to increase, also unsuitable very few, causing that lithium-ion capacitor capacity reduces to avoid lithium-inserting amount not enough, general, the mass ratio of described lithium net and described negative electrode active material is 0.05-0.1:1.
In order to increase the uniformity to the embedding lithium in negative plate surface, the laying area of described lithium net is more than the area of described negative electrode active material layer, the entire area of lithium net can make negative electrode active material layer be completely covered by lithium net more than the area of negative electrode active material layer, and anticathode sheet fully mends lithium.
The porosity of lithium net can optionally be mended the amount of lithium and be arranged, in amount one timing of required benefit lithium, it is possible to by the porosity of adjustment lithium net so that lithium net can be completely covered negative plate surface, general, the porosity of described lithium net is 25-75%.
Negative electrode active material layer includes negative electrode active material, and negative electrode active material is negative electrode active material commonly used in the art, one or several in graphite, hard carbon, soft carbon, carbonaceous mesophase spherules.
In order to make negative electrode active material be combined in better on negative current collector, described negative electrode active material layer also includes binding agent, this binding agent is binding agent commonly used in the art, one or more in Kynoar (PVDF), politef (PTFE), LA132, butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC). Wherein, butadiene-styrene rubber and carboxymethyl cellulose use simultaneously.
In order to improve the electric conductivity of negative electrode active material layer, described negative electrode active material layer also includes conductive agent, and this conductive agent is conductive agent commonly used in the art, the one in SuperP, KS-6, Graphene.
Negative electrode active material in described negative electrode active material layer, conductive agent, binding agent mass percent be: negative electrode active material 85-90%, conductive agent 3-5%, binding agent 5-10%.
The thickness of described negative plate is 120-220 ��m.
The technical scheme of the preparation method of the lithium-ion capacitor negative pole unit of the present invention is as follows:
The preparation method of above-mentioned lithium-ion capacitor negative pole unit, comprises the steps:
Lithium net and negative plate are stacked, roll-in, to obtain final product.
The lithium-ion capacitor negative pole unit that the preparation method of the lithium-ion capacitor negative pole unit of the present invention prepares, the embedding lithium of cathode pole piece is uniformly, good product consistency, the pre-embedding lithium time is short, working (machining) efficiency is high.
Described negative plate prepares as follows: negative electrode active material, conductive agent and binding agent Homogeneous phase mixing are made cathode size, is coated in negative pole currect collecting surface, 100-150 DEG C of drying, roll-in, point bar, to obtain final product.
Rolling pressure is can make lithium net secure fit be advisable on negative plate surface, general, and in order to make lithium net maximize with negative plate contact area, the pressure of described roll-in is 50-200kg/cm2��
The technical scheme of the lithium-ion capacitor of the present invention is as follows:
A kind of lithium-ion capacitor, including positive pole, negative pole, described negative pole is above-mentioned lithium-ion capacitor negative pole unit.
Described just extremely positive plate, positive plate includes plus plate current-collecting body and is coated in the positive active material of anode collection surface. Also include binding agent and conductive agent. Described positive active material, conductive agent, binding agent mass ratio be 85:7:8.
Described positive active material is activated carbon. Described binding agent is binding agent commonly used in the art, one or more in Kynoar (PVDF), politef (PTFE), LA132, butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC). Wherein, butadiene-styrene rubber and carboxymethyl cellulose use simultaneously. This conductive agent is conductive agent commonly used in the art, the one in SuperP, KS-6, Graphene.
The thickness of positive plate and the thickness of negative plate match, it is ensured that positive pole, capacity of negative plates mate, and general, the thickness of described positive plate is 200-350 ��m.
Described lithium-ion capacitor also includes barrier film and electrolyte.
Described barrier film is a kind of or several composite membrane being composited therein in cellulose, polypropylene, polyethylene.
Described lithium-ion capacitor also includes electrolyte, described electrolyte includes lithium salts and solvent, described lithium salts is lithium hexafluoro phosphate or LiBF4, the concentration of lithium salts is 1.0-1.2mol/L, and described solvent is one or several in Allyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate.
Above-mentioned lithium-ion capacitor prepares as follows: by positive pole, barrier film, negative pole makes takeup type battery core, enter shell, fluid injection, stand 4h, and record maximum voltage value, it is used for judging the degree of depth of pre-embedding lithium, specifically adopt with the following method: after injecting electrolyte, lithium metal and negative pole direct short-circuit, metal-lithium ion also embeds in negative material, respective negative potential voltage reduces, and lithium current potential can be maintained about 3.0V by lithium-ion capacitor anode activated charcoal, so reaching 2.8-3.0V by the voltage of test capacitors namely can determine whether that negative pole prelithiation completes, then at 1.5A constant-current charge to 3.8V, 3.8V constant voltage 24h is melted into, aerofluxus, obtain.
The lithium-ion capacitor of the present invention utilizes lithium net to carry out negative pole and mends lithium, and electrolyte can quickly infiltrate, and whole lithium metals can realize electrochemistry short circuit with negative pole, every layer of cathode pole piece can both uniform embedding lithium, the concordance of product is greatly improved.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is further detailed.
Embodiment 1
The lithium-ion capacitor negative pole unit of the present embodiment includes negative plate, negative plate includes negative current collector Copper Foil and is coated in the negative electrode active material layer on two surfaces of negative current collector, negative electrode active material layer is by negative electrode active material hard carbon, conductive agent SuperP, binding agent Kynoar (PVDF) is uniformly mixed according to mass ratio 90:3:7, the thickness of negative plate is 200 ��m, the negative electrode active material layer surface on negative plate two sides is all equipped with lithium net, the porosity of lithium net is 25%, the mass ratio of lithium net and negative electrode active material is 0.05:1, the entirety of lithium net lays the area area more than negative plate surface negative electrode active material layer being completely covered by negative electrode active material layer.
The preparation method of the lithium-ion capacitor negative pole unit of the present embodiment comprises the steps:
1) negative electrode active material hard carbon, conductive agent SuperP and binding agent Kynoar are added solvent NMP Homogeneous phase mixing and make cathode size, adopt coater on two surfaces of negative current collector Copper Foil, 120 DEG C of drying, roll-in, point bar, obtain negative plate;
2) lithium net is overlayed step 1) in prepare negative plate surface, at 50kg/cm2Pressure under roll-in, to obtain final product.
The lithium-ion capacitor of the present embodiment includes positive pole, negative pole, barrier film and electrolyte, and barrier film is arranged between a positive electrode and a negative electrode, and negative pole uses above-mentioned lithium-ion capacitor negative pole unit.
Above-mentioned just extremely positive plate, positive plate includes plus plate current-collecting body aluminium foil and is coated in the positive electrode active material layer on two surfaces of plus plate current-collecting body, and positive electrode active material layer is uniformly mixed according to mass ratio 85:7:8 by positive electrode active material activated carbon, conductive agent SuperP, polyfluortetraethylene of binding element (PTFE). This positive plate prepares by the following method: positive electrode active material activated carbon, conductive agent SuperP, polyfluortetraethylene of binding element (PTFE) is added solvent deionized water Homogeneous phase mixing and makes anode sizing agent, adopt coater on plus plate current-collecting body aluminium foil, dry at 120 DEG C, coating thickness after drying is 260 ��m, roll-in, positive plate thickness after roll-in is 120 ��m, trimming, cut-parts, point bar, rolling, prepares positive plate.
Barrier film is microporous polypropylene membrane, and electrolyte includes lithium salts lithium hexafluoro phosphate and solvent, and the concentration of lithium hexafluoro phosphate is 1.0mol/L, and solvent is mixed according to volume ratio 3:1:4 by ethylene carbonate, Allyl carbonate, dimethyl carbonate.
The lithium-ion capacitor of the present embodiment prepares as follows: positive pole, barrier film, negative pole are made takeup type battery core, enter shell, fluid injection, stands 4h, and records maximum voltage value, it is used for judging the degree of depth of pre-embedding lithium, with 2.8-2.9V for qualified, then 1.5A constant-current charge is melted into 3.8V, 3.8V constant voltage 24h, aerofluxus, to obtain final product.
Embodiment 2
The lithium-ion capacitor negative pole unit of the present embodiment includes negative plate, negative plate includes negative current collector Copper Foil and is coated in the negative electrode active material layer on two surfaces of negative current collector, negative electrode active material layer is by negative electrode active material hard carbon, conductive agent SuperP, polyfluortetraethylene of binding element (PTFE) is uniformly mixed according to mass ratio 86:5:9, the thickness of negative plate is 200 ��m, the negative electrode active material layer surface on negative plate two sides is all equipped with lithium net, the porosity of lithium net is 50%, the mass ratio of lithium net and negative electrode active material is 0.08:1, the entirety of lithium net lays the area area more than negative plate surface negative electrode active material layer being completely covered by negative electrode active material layer.
The preparation method of the lithium-ion capacitor negative pole unit of the present embodiment comprises the steps:
1) negative electrode active material hard carbon, conductive agent SuperP and binding agent Kynoar are added solvent NMP Homogeneous phase mixing and make cathode size, adopt coater on two surfaces of negative current collector Copper Foil, 120 DEG C of drying, roll-in, point bar, obtain negative plate;
2) lithium net is overlayed step 1) in prepare negative plate surface, at 100kg/cm2Pressure under roll-in, to obtain final product.
The lithium-ion capacitor of the present embodiment includes positive pole, negative pole, barrier film and electrolyte, and barrier film is arranged between a positive electrode and a negative electrode, and negative pole uses above-mentioned lithium-ion capacitor negative pole unit.
Above-mentioned just extremely positive plate, positive plate includes plus plate current-collecting body aluminium foil and is coated in the positive electrode active material layer on two surfaces of plus plate current-collecting body, and positive electrode active material layer is uniformly mixed according to mass ratio 85:7:8 by positive electrode active material activated carbon, conductive agent SuperP, polyfluortetraethylene of binding element (PTFE). This positive plate prepares by the following method: positive electrode active material activated carbon, conductive agent SuperP, polyfluortetraethylene of binding element (PTFE) is added solvent deionized water Homogeneous phase mixing and makes anode sizing agent, adopt coater on plus plate current-collecting body aluminium foil, dry at 120 DEG C, coating thickness after drying is 260 ��m, roll-in, positive plate thickness after roll-in is 120 ��m, trimming, cut-parts, point bar, rolling, prepares positive plate.
Barrier film is polyethene microporous membrane, and electrolyte includes lithium salts lithium hexafluoro phosphate and solvent, and the concentration of lithium hexafluoro phosphate is 1.0mol/L, and solvent is mixed according to volume ratio 3.5:0.5:4 by ethylene carbonate, Allyl carbonate, diethyl carbonate.
The lithium-ion capacitor of the present embodiment prepares as follows: positive pole, barrier film, negative pole are made lamination type electric core, enter shell, fluid injection, stands 4h, and records maximum voltage value, it is used for judging the degree of depth of pre-embedding lithium, with 2.8-2.9V for qualified, then it is melted into 1.5A constant-current charge to 3.8V, 3.8V constant voltage 24h, aerofluxus, to obtain final product.
Embodiment 3
The lithium-ion capacitor negative pole unit of the present embodiment includes negative plate, negative plate includes negative current collector Copper Foil and is coated in the negative electrode active material layer on two surfaces of negative current collector, negative electrode active material layer is by negative electrode active material hard carbon, conductive agent SuperP, hybrid adhesive is uniformly mixed according to mass ratio 90:3:7, hybrid adhesive is mixed according to mass ratio 5:3 by butadiene-styrene rubber (SBR) and carboxymethyl cellulose (CMC), the thickness of negative plate is 200 ��m, the negative electrode active material layer surface on negative plate two sides is all equipped with lithium net, the porosity of lithium net is 70%, the mass ratio of lithium net and negative electrode active material is 0.1:1, the entirety of lithium net lays the area area more than negative plate surface negative electrode active material layer being completely covered by negative electrode active material layer.
The preparation method of the lithium-ion capacitor negative pole unit of the present embodiment comprises the steps:
1) negative electrode active material hard carbon, conductive agent SuperP and binding agent Kynoar are added solvent NMP Homogeneous phase mixing and make cathode size, adopt coater on two surfaces of negative current collector Copper Foil, 150 DEG C of drying, roll-in, point bar, obtain negative plate;
2) lithium net is overlayed step 1) in prepare negative plate surface, at 200kg/cm2Pressure under roll-in, to obtain final product.
The lithium-ion capacitor of the present embodiment includes positive pole, negative pole, barrier film and electrolyte, and barrier film is arranged between a positive electrode and a negative electrode, and negative plate uses above-mentioned lithium-ion capacitor negative pole unit.
Above-mentioned just extremely positive plate, positive plate includes plus plate current-collecting body aluminium foil and is coated in the positive electrode active material layer on two surfaces of plus plate current-collecting body, and positive electrode active material layer is uniformly mixed according to mass ratio 85:7:8 by positive electrode active material activated carbon, conductive agent SuperP, polyfluortetraethylene of binding element (PTFE). This positive plate prepares by the following method: positive electrode active material activated carbon, conductive agent SuperP, polyfluortetraethylene of binding element (PTFE) is added solvent deionized water Homogeneous phase mixing and makes anode sizing agent, adopt coater on plus plate current-collecting body aluminium foil, dry at 120 DEG C, coating thickness after drying is 260 ��m, roll-in, positive plate thickness after roll-in is 120 ��m, trimming, cut-parts, point bar, rolling, prepares positive plate.
Barrier film is microporous polypropylene membrane, and electrolyte includes lithium salts lithium hexafluoro phosphate and solvent, and the concentration of lithium hexafluoro phosphate is 1.2mol/L, and solvent is mixed according to volume ratio 3:1:4 by ethylene carbonate, Allyl carbonate, dimethyl carbonate.
The lithium-ion capacitor of the present embodiment prepares as follows: positive pole, barrier film, negative pole are made lamination type electric core, enter shell, fluid injection, stands 4h, and records maximum voltage value, it is used for judging the degree of depth of pre-embedding lithium, with 2.8-2.9V for qualified, then it is melted into 1.5A constant-current charge to 3.8V, 3.8V constant voltage 24h, aerofluxus, to obtain final product.
Negative electrode active material kind in embodiment 4-9 and lithium net are as shown in table 1 with the mass ratio of negative electrode active material, other all identical with embodiment 1.
The mass ratio of negative electrode active material kind in table 1 embodiment 4-9 and lithium net and negative electrode active material
Note: Li/NaMass ratio for lithium net Yu negative electrode active material.
Experimental example
The lithium-ion capacitor obtained in embodiment 1-9 is tested as follows:
(1) static capacity and energy density test.
At 20-30 DEG C, charge to 4.0V with 10A, shelve 15s, be then discharged to 2.0V with 10A, circulate 5 weeks, average. Test result is as shown in table 2.
(2) cycle life test.
At 20-30 DEG C, in the voltage range of 2.0-4.0V, with 15A constant current charge-discharge, circulate 100,000 times, and calculate the last discharge capacity conservation rate relative to discharge capacity first. Test result is as shown in table 2.
(3) DC-Life test.
At 65 DEG C, continuing to charge with constant voltage 4.0V, then 15A constant-current discharge is to 2V, 15A constant-current charge is to 4V again, circulating 3 weeks, less than 80% or the internal resistance being down to initial capacity with the 3rd week discharge capacity increases to the 200% of initial value for stop condition, and records the time of 4.0V constant voltage test. Test result is as shown in table 2.
Lithium-ion capacitor test result in table 2 embodiment 1-9
Note: Li/NaFor lithium net and negative electrode active material mass ratio.
As can be seen from the above table, the energy density of the lithium-ion capacitor of the present invention is higher, the maximum 28.4Wh/kg that reaches of energy density, and after circulating 100,000 times, capability retention still reaches 81%-89%, 4.0V, DC-Life test result maximum duration reaches 2100 hours at 65 DEG C.
Claims (10)
1. a lithium-ion capacitor negative pole unit, including negative plate, described negative plate includes negative current collector and is coated in the negative electrode active material layer of negative pole currect collecting surface, it is characterised in that described negative electrode active material layer surface is equipped with lithium net.
2. lithium-ion capacitor negative pole unit as claimed in claim 1, it is characterised in that the mass ratio of described lithium net and described negative electrode active material is 0.05-0.1:1.
3. lithium-ion capacitor negative pole unit as claimed in claim 1, it is characterised in that the laying area of described lithium net is more than the area of described negative electrode active material layer.
4. lithium-ion capacitor negative pole unit as claimed in claim 1, it is characterised in that the porosity of described lithium net is 25-75%.
5. lithium-ion capacitor negative pole unit as claimed in claim 1, it is characterised in that described negative electrode active material layer includes negative electrode active material, and described negative electrode active material is one or several in graphite, hard carbon, soft carbon, carbonaceous mesophase spherules.
6. lithium-ion capacitor negative pole unit as claimed in claim 1, it is characterised in that the thickness of described negative plate is 120-220 ��m.
7. the preparation method of lithium-ion capacitor negative pole unit as claimed in claim 1, it is characterised in that including: lithium net and negative plate are stacked, roll-in, to obtain final product.
8. the preparation method of lithium-ion capacitor negative pole unit as claimed in claim 7, it is characterised in that the pressure of described roll-in is 50-200kg/cm2��
9. a lithium-ion capacitor, including positive pole, negative pole, it is characterised in that described negative pole is the lithium-ion capacitor negative pole unit as described in claim 1-6 any one.
10. lithium-ion capacitor as claimed in claim 9, it is characterized in that, described positive pole includes plus plate current-collecting body and is coated in the positive electrode active material layer of anode collection surface, and described positive electrode active material layer includes positive active material, and described positive active material is activated carbon.
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| CN107731555A (en) * | 2017-10-24 | 2018-02-23 | 中国科学院电工研究所 | A kind of preparation method of lithium-ion capacitor |
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| CN110896140A (en) * | 2018-09-13 | 2020-03-20 | 宁德时代新能源科技股份有限公司 | Lithium-rich negative plate, battery cell and lithium ion battery |
| CN112331928A (en) * | 2019-08-05 | 2021-02-05 | 宁德时代新能源科技股份有限公司 | Negative electrode lithium-supplementing pole piece and lithium ion battery |
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| CN106229542A (en) * | 2016-08-19 | 2016-12-14 | 洛阳力容新能源科技有限公司 | A kind of lithium ion battery battery core and preparation method thereof, lithium ion battery |
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| CN107731555B (en) * | 2017-10-24 | 2019-02-01 | 中国科学院电工研究所 | A kind of production method of lithium-ion capacitor |
| CN110896140A (en) * | 2018-09-13 | 2020-03-20 | 宁德时代新能源科技股份有限公司 | Lithium-rich negative plate, battery cell and lithium ion battery |
| CN110896140B (en) * | 2018-09-13 | 2021-01-15 | 宁德时代新能源科技股份有限公司 | Lithium-rich negative plate, battery cell and lithium ion battery |
| CN110164701A (en) * | 2019-06-06 | 2019-08-23 | 合肥羿振电力设备有限公司 | A kind of lithium-ion capacitor and preparation method thereof |
| CN112331928A (en) * | 2019-08-05 | 2021-02-05 | 宁德时代新能源科技股份有限公司 | Negative electrode lithium-supplementing pole piece and lithium ion battery |
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| CN105655147B (en) | 2018-04-17 |
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