CN114743803A - High-voltage hybrid lithium ion supercapacitor and preparation method thereof - Google Patents
High-voltage hybrid lithium ion supercapacitor and preparation method thereof Download PDFInfo
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- CN114743803A CN114743803A CN202210344177.8A CN202210344177A CN114743803A CN 114743803 A CN114743803 A CN 114743803A CN 202210344177 A CN202210344177 A CN 202210344177A CN 114743803 A CN114743803 A CN 114743803A
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Images
Classifications
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- 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
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- 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
- H01G11/32—Carbon-based
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- H—ELECTRICITY
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- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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- H01G11/54—Electrolytes
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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
- H01G11/78—Cases; Housings; Encapsulations; Mountings
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Abstract
The invention discloses a high-voltage hybrid lithium ion supercapacitor and a preparation method thereof. The high-voltage mixed lithium ion supercapacitor comprises a positive plate, a negative plate, a diaphragm between the positive plate and the negative plate, electrolyte filled in gaps between the positive plate and the negative plate and the diaphragm, and a shell, wherein the positive plate and/or the negative plate consists of a current collector and an electrode material coated on the surface of the current collector and comprising a nano carbon material, and the electrolyte is high-voltage electrolyte formed by mixing an organic solvent, a lithium salt and an additive. The preparation method of the high-voltage hybrid lithium ion supercapacitor comprises the steps of high-voltage electrolyte preparation, positive plate preparation, negative plate preparation and packaging. According to the invention, the nano carbon material is introduced to carry out composite modification on the 5V positive electrode material and the porous carbon material, and the capacitor has higher working voltage, energy density, power density, safety and cycle service life by optimizing the electrolyte and optimizing the positive electrode capacity ratio and the negative electrode capacity ratio of the capacitor.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a high-voltage hybrid lithium ion supercapacitor with high working voltage, energy density, power density, safety and cycle service life and a preparation method thereof.
Background
Since the 20 th century, the development of economy has been rapidly advanced, the resources are about to be exhausted, the pollution is becoming serious, and the search for novel renewable energy sources capable of replacing fossil fuels such as petroleum, coal, natural gas and the like is urgent. Meanwhile, the rapid development of new energy technologies brings about an urgent need for new energy storage technologies.
Super capacitor (also called electrochemical capacitor) is a new energy storage element between conventional capacitor and chemical battery which is developed and developed in recent decades at home and abroad. Due to its higher power density (10)3~104Wkg-1) And ultra-long cycle life (up to tens of thousands of times), and a wide working temperature range (-40-70 ℃), and the super capacitor has been widely applied to the fields of transportation, renewable energy, industrial and consumer electronics products, and the like.
The super capacitor in commercial use at present is mainly an organic electric double layer capacitor composed of two symmetrical Activated Carbon (AC) electrodes and an organic electrolyte, and the electric double layer at the interface of the AC electrode and the electrolyte is used for storing electric energy, for example, patent Z1992084601, CN 1229517A. The working voltage of the super capacitor is only 2.7V, and the energy density is relatively low (<10Whkg-1) Limiting further applications and developments thereof.
Energy formula E =0.5CV according to super capacitor2Sum power formula P = V2It is known that the specific capacity C and the operating voltage V can be improved in terms of the energy density and the power density. The specific capacity C of the capacitor can be improved by improving the performance (such as specific surface area, aperture and aperture distribution, granularity and granularity distribution and the like) of an electrode material or packaging the capacitor by adopting an asymmetric mixed structure; further, the asymmetric hybrid structure results in a higher operating voltage of the capacitor, thereby increasing the energy density and power density of the resulting capacitor.
Lithium ion batteries have higher operating voltages and energy densities than electric double layer capacitors. The combination of the positive electrode material of the lithium ion battery and the active carbon electrode of the electric double layer capacitor to form the hybrid lithium ion super capacitor is an important direction for researching and developing the super capacitor with high energy density in recent years. The device generally adopts the anode of a lithium ion battery to replace the active carbon anode of a double electric layer capacitor, and the anode and the active carbon cathode form a hybrid lithium ion super capacitor. The charge and discharge of the lithium ion battery material mainly relate to reversible intercalation/deintercalation of lithium ions, and the charge and discharge of the activated carbon material still belong to an electric double layer mechanism of ion adsorption/desorption, so that the hybrid lithium ion super capacitor constructed in the way has the characteristics of both the lithium ion battery and the electric double layer capacitor, and shows higher power density than the lithium ion battery and higher working voltage and energy density than the electric double layer capacitor. Common positive electrode materials for lithium ion batteries, such as lithium cobaltate (LiCoO)2) Lithium manganate (LiMn)2O4) Lithium iron phosphate (LiFePO)4) Ternary materials (NCM), have been used in the research and development of hybrid lithium ion supercapacitors. However, limited by the limited lithium insertion potential (about 4V) of such positive electrode materialsvs.Li/Li+) The working voltage (2.0-3.0V), the energy density and the power density of the obtained hybrid lithium ion super capacitor have to be advancedThe process is improved by one step.
In the research of novel positive electrode materials of lithium ion batteries, the charge-discharge platform is generally set at 4.5V (V) ((R))vs.Li/Li+) The above materials are referred to as high potential positive electrode materials, or 5V positive electrode materials. According to the current research results, the high-potential cathode material mainly comprises spinel type LiMxMn2-xO4(x is more than 0 and less than 1, M is transition metal elements such as iron, copper, cobalt, nickel, chromium and the like), olivine material LiMPO4(M is a transition metal element such as manganese, cobalt, nickel, or chromium), and a lithium-rich manganese-based material xLi having a layered structure2MnO3•（1-x）LiMO2(x is more than 0 and less than 1, and M is transition metal elements such as manganese, cobalt, nickel and the like). With the development and utilization of these 5V novel high potential lithium ion battery cathode materials, great attention has been paid to the application research of hybrid lithium ion supercapacitors. The material has higher potential, so that the working voltage, the energy density and the power density of the super capacitor can be greatly improved. Among them, spinel LiNi0.5Mn1.5O4The (LNMO) positive electrode material is in LiMn2O4Developed on the basis of (1), it has higher potential (4.7V)vs.Li/Li+) Higher theoretical capacity (147 mAhg)-1) The lithium ion battery positive electrode material has the characteristics of good safety, low cost, rich resources, no toxicity and the like, is considered to be one of the most potential lithium ion battery positive electrode materials of the next generation, and has been used for application research of a hybrid lithium ion supercapacitor. For example, in 2005, Li et al combined an LNMO positive electrode with an activated carbon negative electrode and a conventional carbonate electrolyte to prepare a Hybrid lithium Ion capacitor with a working voltage of 2.8V (h.li, l.cheng, and y.xia, a Hybrid Electrochemical super capacitor base 5V Li-Ion Battery capacitor,Electrochem.Solid-StateLett.8, a433 (2005)); in 2014, Adrian Brandt et al encapsulated a hybrid capacitor with the same electrode material and electrolyte and increased its operating voltage to 3.3V (A.Brandt, A.Balducci, U.Rodehorst, S.Menne, M.winter, and A.Bhaskan, investments around the use of the Degradation Mechanism of LiNi0.5Mn1.5O4ina HighPower LIC，J.Electrochem.Soc.161, a1139 (2014)). However, the power performance of the resulting capacitor is poor due to the poor rate performance of the conventional LNMO and activated carbon materials used in these studies. On the other hand, the conventional carbonate electrolytes are easy to be electrochemically decomposed when the voltage is higher than 4.4V, and the electrolytes lack proper protective agents for protecting the normal operation of the LNMO at high voltage, so that the operating voltage, the energy density and the power density of the obtained capacitor are still low, the cycle life is short, and the practical application of the hybrid lithium ion supercapacitor based on the LNMO is limited.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides the high-voltage hybrid lithium-ion supercapacitor with higher working voltage, energy density, power density, safety and cycle service life, and also provides the preparation method of the high-voltage hybrid lithium-ion supercapacitor, which has the advantages of simple preparation process, environmental protection and low cost.
The high-voltage hybrid lithium ion super capacitor is realized by the following steps: the lithium ion battery comprises a positive plate, a negative plate, a diaphragm between the positive plate and the negative plate, electrolyte filled in gaps between the positive plate and the negative plate and a shell, wherein the positive plate and/or the negative plate consists of a current collector and an electrode material coated on the surface of the current collector and comprising a nano carbon material, and the electrolyte is high-voltage electrolyte formed by mixing an organic solvent, a lithium salt and an additive.
The preparation method of the high-voltage hybrid lithium ion supercapacitor is realized by the following steps: the method comprises the steps of high-voltage electrolyte preparation, positive plate preparation, negative plate preparation and packaging, and specifically comprises the following steps:
A. preparing a high-voltage electrolyte: under the inert gas atmosphere condition that oxygen is controlled to be less than 1ppm and moisture is controlled to be less than 1ppm, according to a certain mass ratio, uniformly mixing a selected organic solvent, lithium salt and an additive to prepare a high-voltage electrolyte;
B. preparing a positive plate: adding a 5V positive electrode material, a nano carbon material, a conductive agent and a binder into N-methyl pyrrolidone according to a certain mass ratio, stirring at a high speed in vacuum to form positive electrode slurry, uniformly coating the positive electrode slurry on the surface of a current collector, and drying, rolling and cutting to obtain a positive electrode sheet;
C. preparing a negative plate: adding a porous carbon material, a nano carbon material, a conductive agent and a binder into deionized water according to a certain mass ratio, stirring at a high speed in vacuum to form negative electrode slurry, then uniformly coating the negative electrode slurry on the surface of a current collector, and drying, rolling and slitting to prepare a negative electrode sheet;
D. packaging: and packaging the high-voltage electrolyte, the positive plate, the negative plate and the diaphragm under the inert gas atmosphere condition of controlling oxygen to be less than 1ppm and moisture to be less than 1ppm to obtain the high-voltage hybrid lithium ion supercapacitor.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the nano-carbon material is introduced to respectively carry out composite modification on the 5V positive electrode material and the porous carbon material to prepare the nano-composite positive electrode material and the nano-composite negative electrode material, so that the conductivity and rate capability of the 5V positive electrode material and the porous carbon material are improved, and the power characteristic, safety and cycle service life of the capacitor are improved.
2. According to the invention, the organic solvent suitable for the high-voltage electrolyte, the lithium salt electrolyte suitable for the high-voltage electrolyte and the electrolyte additive capable of stabilizing the high-voltage anode material are selected, so that the prepared high-voltage electrolyte is suitable for the high-voltage hybrid lithium ion supercapacitor.
3. According to the invention, the capacitor is packaged by the nano-carbon material composite modified 5V positive electrode material, the porous carbon material negative electrode and the high-voltage electrolyte, and the capacity ratio of the positive electrode and the negative electrode is optimized, so that the charging and discharging processes of the positive electrode and the negative electrode can be better matched, the working voltage of the capacitor is improved and stabilized (reaching more than 3.4V), and the requirement of the high-energy density/high-power density super capacitor is further met.
Therefore, the high-voltage hybrid lithium ion supercapacitor has higher working voltage, energy density, power density, safety and cycle service life, and the preparation method of the high-voltage hybrid lithium ion supercapacitor is simple in process, short in flow, green, environment-friendly, low in cost and suitable for industrial production.
Drawings
FIG. 1 is a cyclic voltammogram of a high voltage electrolyte prepared from example 1;
FIG. 2 is a high power scanning electron micrograph of the positive plate of LNMO/SP/KS/PVDF (80/5/5/10) of the high voltage hybrid lithium ion supercapacitor made from example 2;
FIG. 3 is a high power scanning electron micrograph of the positive electrode plate of LNMO/CNT/SP/KS/PVDF (80/0.3/4.85/4.85/10) of the high voltage hybrid lithium ion supercapacitor prepared from example 2;
FIG. 4 is a high power scanning electron micrograph of the positive plate of LNMO/CNT/SP/KS/PVDF (80/5/2.5/2.5/10) of the high voltage hybrid lithium ion supercapacitor prepared from example 2;
FIG. 5 is a cyclic voltammogram of the LNMO/CNT/SP/KS/PVDF (80/0.3/4.85/4.85/10) positive half cell prepared from example 2;
fig. 6 is a rate test curve for a positive half cell prepared from example 2;
FIG. 7 is a high power scanning electron micrograph of the AC/SP/SBR/CMC (90/5/3/2) negative electrode sheet of the high voltage hybrid lithium ion supercapacitor prepared from example 3;
FIG. 8 is a high power scanning electron micrograph of the AC/CNT/SP/SBR/CMC (90/0.625/4.375/3/2) negative electrode sheet of the high voltage hybrid lithium ion supercapacitor made from example 3;
FIG. 9 is a high power scanning electron micrograph of the AC/CNT/CMC (90/5/3/2) negative electrode sheet of the high voltage hybrid lithium ion supercapacitor made from example 3;
FIG. 10 is a cyclic voltammogram of the AC/CNT/SP/SBR/CMC (90/0.625/4.375/3/2) negative half-cell prepared from example 3;
fig. 11 is a rate test curve for an anode half cell prepared from example 3;
FIG. 12 is a cyclic voltammogram of the high voltage hybrid lithium ion supercapacitor packaged in example 4 at a voltage range of 0-3.5V;
FIG. 13 is a graph showing the cycle life of the high voltage hybrid lithium ion supercapacitor packaged in example 4 under a voltage range of 0-3.45V;
FIG. 14 is a high power scanning electron micrograph of an electrode sheet of a conventional symmetric electric double layer supercapacitor prepared from comparative example 1;
FIG. 15 is a cyclic voltammogram of a conventional symmetric double electric layer supercapacitor packaged by comparative example 1 at a voltage range of 0 to 2.7V;
FIG. 16 is a cycle life test chart of the conventional symmetrical double electric layer supercapacitor packaged by comparative example 1 at a voltage range of 0 to 2.7V;
fig. 17 is a graph of energy density versus power density for a high voltage hybrid lithium ion supercapacitor packaged in example 4 and a conventional symmetric electric double layer supercapacitor packaged in comparative example 1.
Detailed Description
The invention is further described with reference to the following figures and examples, but the invention is not limited in any way and any variations or modifications based on the teachings of the invention are within the scope of the invention.
The high-voltage mixed lithium ion supercapacitor comprises a positive plate, a negative plate, a diaphragm between the positive plate and the negative plate, electrolyte filled in gaps between the positive plate and the negative plate and the diaphragm, and a shell, wherein the positive plate and/or the negative plate consists of a current collector and an electrode material coated on the surface of the current collector and comprising a nano carbon material, and the electrolyte is a high-voltage electrolyte formed by mixing an organic solvent, a lithium salt and an additive.
The electrode material of the positive plate consists of a 5V positive material, a nano carbon material, a conductive agent and a binder, the electrode material of the negative plate consists of a porous carbon material, a nano carbon material, a conductive agent and a binder, and the nano carbon material is at least one of a carbon nano tube, carbon nano fiber and graphene.
The kind of the carbon nanotube is not limited, and may be a single-walled carbon nanotube (SWCNT) and/or a multi-walled carbon nanotube (MWCNT); the kind of the carbon nanofiber is not limited; the type of the graphene is not limited, and may be single-layer graphene and/or multi-layer graphene.
The conductive agent is at least one of conductive graphite, conductive carbon black and conductive carbon fiber.
The binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, styrene butadiene rubber and acrylic resin.
The current collector is one or an alloy of at least any two of sheet, net or foam Cu, Al, Ni and Ag.
The current collector is a corrosion aluminum foil, a porous aluminum foil, a carbon-coated aluminum foil or a plain aluminum foil.
The diaphragm is at least one of a polypropylene porous film, a polyethylene porous film, a polypropylene/polyethylene composite porous film, a cellulose acetate porous diaphragm, a glass fiber porous film, nylon and asbestos paper.
The 5V anode material is spinel type LiMxMn2-xO4Olivine-type material LiNPO4Lithium-rich manganese-based material xLi with laminated structure2MnO3•（1-x）LiYO2At least one of, wherein: 0 < x <1, M = Fe, Cu, Co, Ni, Cr, N = Mn, Co, Ni, Cr, Y = Mn, Co, Ni.
The content of each substance in the electrode material of the positive plate is as follows by mass percent: 50-97.99% of 5V positive electrode material, 0.01-10% of nano carbon material, 1-50% of conductive agent and 1-50% of binder.
The porous carbon material is at least one of activated carbon powder, activated carbon cloth, activated carbon fiber, a nano carbon material, carbon aerogel, porous graphite and porous hard carbon, and the content of each substance in the electrode material of the negative plate is as follows by mass percent: 50-97.99% of porous carbon material, 0.01-10% of nano carbon material, 1-50% of conductive agent and 1-50% of binder.
The capacity ratio of the positive electrode to the negative electrode of the high-voltage hybrid lithium ion super capacitor is 1: 1-10: 1.
The concentration of lithium salt in the high-voltage electrolyte is 0.1-10 mol L-1The lithium salt is lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Lithium bis (oxalato) borate (LiBOB), LiBF4Lithium tetrafluoroborate, lithium difluorooxalato borate (LiODFB), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium difluorophosphate (LiPO)2F2) And lithium difluorooxalate phosphate (LiODFP).
The high-voltage electrolyte comprises 0.01-10% of additives by mass percent, wherein the additives are triphenyl phosphite (TPPi), lithium oxalato borate (LiBOB), lithium difluoroborate oxalate (LiODFB), lithium fluorobis (malonate) borate (LiBMB), lithium difluorosulfate borate (LiBSO)4F2) At least one of trifluoromethylphenylsulfide (PTS) and trimethyl borate (TMB).
The organic solvent in the high-voltage electrolyte is at least one of Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), Propylene Carbonate (PC), fluoroethylene carbonate (FEC), fluoropropylene carbonate (TFPC), Gamma Butyrolactone (GBL), Gamma Valerolactone (GVL), N-Dimethylformamide (DMF), Acetonitrile (AN) and Fluoroacetonitrile (FAN).
The high-voltage hybrid lithium ion super capacitor is packaged in any one of button type, cylindrical type, square type and special shape, and the high-voltage hybrid lithium ion super capacitor is packaged in any one of a steel shell, a plastic shell, an aluminum shell and an aluminum plastic film.
The preparation method of the high-voltage hybrid lithium ion supercapacitor comprises the steps of high-voltage electrolyte preparation, positive plate preparation, negative plate preparation and packaging, and specifically comprises the following steps:
A. preparing a high-voltage electrolyte: under the inert gas atmosphere condition that oxygen is controlled to be less than 1ppm and moisture is controlled to be less than 1ppm, uniformly mixing selected organic solvent, lithium salt and additive according to a certain mass ratio to prepare high-voltage electrolyte;
B. preparing a positive plate: adding a 5V positive electrode material, a nano carbon material, a conductive agent and a binder into N-methyl pyrrolidone according to a certain mass ratio, stirring at a high speed in vacuum to form positive electrode slurry, uniformly coating the positive electrode slurry on the surface of a current collector, and drying, rolling and cutting to obtain a positive electrode sheet;
C. preparing a negative plate: adding a porous carbon material, a nano carbon material, a conductive agent and a binder into deionized water according to a certain mass ratio, stirring at a high speed in vacuum to form negative electrode slurry, then uniformly coating the negative electrode slurry on the surface of a current collector, and drying, rolling and cutting to obtain a negative electrode sheet;
D. packaging: and packaging the high-voltage electrolyte, the positive plate, the negative plate and the diaphragm under the inert gas atmosphere condition of controlling oxygen to be less than 1ppm and moisture to be less than 1ppm to obtain the high-voltage hybrid lithium ion supercapacitor.
The concentration of lithium salt in the high-voltage electrolyte prepared in the step A is 0.1-10 mol L-1And/or the content of the additive is 0.01-10% by mass.
And the organic solvent in the step A is at least one of Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), Propylene Carbonate (PC), fluoroethylene carbonate (FEC), fluoropropylene carbonate (TFPC), Gamma Butyrolactone (GBL), Gamma Valerolactone (GVL), N-Dimethylformamide (DMF), Acetonitrile (AN) and Fluoro Acetonitrile (FAN).
The lithium salt in the step A is lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Lithium bis (oxalato) borate (LiBOB) and LiBF4Lithium tetrafluoroborate, lithium difluorooxalato borate (LiODFB), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium difluorophosphate (LiPO)2F2) And lithium difluorooxalate phosphate (LiODFP).
The additive in the step A is triphenyl phosphite (TPPi), lithium oxalate borate (LiBOB), lithium difluoro borate oxalate (LiODFB), lithium fluoro bis (malonate) borate (LiBMB), lithium difluoro sulfate borate (LiBSO)4F2) Trifluoromethylphenylsulfide (PTS)) And trimethyl borate (TMB).
In the step B, the 5V positive electrode material is a spinel type material LiMxMn2-xO4Olivine-type material LiNPO4Lithium-rich manganese-based material xLi with layered structure2MnO3•（1-x）LiYO2At least one of, wherein: 0 < x <1, M = Fe, Cu, Co, Ni, Cr, N = Mn, Co, Ni, Cr, Y = Mn, Co, Ni.
The content of each substance in the step B is as follows according to mass percent: 50-97.99% of 5V positive electrode material, 0.01-10% of nano carbon material, 1-50% of conductive agent and 1-50% of binder.
And C, the content of each substance in the step C is as follows according to mass percentage: 50-97.99% of porous carbon material, 0.01-10% of nano carbon material, 1-50% of conductive agent and 1-50% of binder.
And C, the porous carbon material in the step C is at least one of activated carbon powder, activated carbon cloth, activated carbon fiber, a nano carbon material, carbon aerogel, porous graphite and porous hard carbon.
And the conductive agent in the step B and/or the step C is at least one of conductive graphite, conductive carbon black and conductive carbon fiber.
And the binder in the step B and/or the step C is at least one of polytetrafluoroethylene, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, styrene butadiene rubber and acrylic resin.
And the nano carbon material in the step B and/or the step C is at least one of carbon nano tube, carbon nano fiber and graphene.
And the current collector in the step B and/or the step C is one or an alloy of at least any two of sheet, net or foam Cu, Al, Ni and Ag.
And D, the capacity ratio of the positive electrode to the negative electrode of the high-voltage hybrid lithium ion super capacitor is 1: 1-10: 1.
Example 1
The invention relates to preparation and test of a high-voltage electrolyte of a high-voltage hybrid lithium ion supercapacitor.
(1) Containing 1mol L-1LiPF6And 0.2% of TPPiPreparation of EC: DMC: EMC (1:1:1) high Voltage electrolyte
In the control of oxygen (<1 ppm) and water (<1 ppm) in a glove box, uniformly mixing and stirring selected organic solvents of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) according to a volume ratio of 1:1:1 to obtain a required mixed solvent; accurately weighing a certain mass of lithium salt lithium hexafluorophosphate (LiPF)6) And triphenyl phosphite (TPPi) as additive are added into the mixed solvent, dissolved and stirred evenly, then a certain amount of molecular sieve is added, and after standing for 24 hours, the mixed solvent containing 1mol L is obtained-1LiPF6And 0.2% TPPi of a high voltage electrolyte.
(2) Testing of the electrolyte
A glassy carbon electrode is taken as a working electrode, a lithium sheet is taken as a reference electrode, a platinum net is taken as a counter electrode, and 5mVs is taken-1The cyclic voltammetry test is carried out on the high-voltage electrolyte at the scanning speed (as shown in the attached figure 1); the test result shows that: the oxidative decomposition of the solvent in the electrolyte occurs at a relatively high potential (6.6V)vs.Li/Li+) That is, the electrolyte has a wide safe electrochemical window; the oxidation peak that begins to appear at 4.2V corresponds to the oxidation of the additive TPPi, indicating that it is capable of oxidizing and forming an effective protective film on the electrode surface before the oxidative decomposition of the solvent of the electrolyte.
Example 2
The invention relates to a preparation and a test of a positive plate of a high-voltage hybrid lithium ion super capacitor.
1. Preparation of high-voltage hybrid lithium ion super capacitor positive plate
(1) Preparation of LNMO/SP/KS/PVDF (80/5/5/10) Pole piece
The method comprises the following steps: accurately weighing polyvinylidene fluoride (PVDF) powder with a certain mass, adding the PVDF powder into a vacuum stirring tank, adding N-methylpyrrolidone (NMP) with a certain mass (the mass ratio of the PVDF to the NMP is 1: 20), setting the rotating speed of a vacuum stirrer to be 500r/min, and stirring at room temperature for 60min to prepare a mixed solution of the PVDF and the NMP; adding a certain mass of 5V anode material LiNi0.5Mn1.5O4(LNMO) and stirring for 90min to obtain LNMO,Mixed slurry of PVDF and NMP; respectively adding certain mass of conductive carbon black (SP) and conductive graphite (KS), and stirring for 60min to prepare the uniformly dispersed positive electrode material electrode slurry with the mass ratio of LNMO/SP/KS/PVDF being 80:5:5: 10.
Step two: vacuumizing and standing the positive electrode material electrode slurry for 10min, filtering by using a 120-mesh filter sieve, and coating the electrode slurry on an aluminum foil current collector according to a certain thickness to obtain a pole piece; vacuum drying the obtained pole piece at 80 ℃ for 3-6 h, and then rolling according to a rolling ratio of 36%; and then, slicing the rolled pole piece by using a slicer to obtain a circular pole piece with the diameter of 12mm, and then carrying out vacuum drying for 10-12 h at 120 ℃ to obtain the positive plate electrode of the high-voltage mixed lithium ion supercapacitor.
(2) Preparation of LNMO/CNT/SP/KS/PVDF (80/0.3/4.85/4.85/10) pole piece
The method comprises the following steps: accurately weighing polyvinylidene fluoride (PVDF) powder with a certain mass, adding the PVDF powder into a vacuum stirring tank, adding N-methylpyrrolidone (NMP) with a certain mass (the mass ratio of the PVDF to the NMP is 1: 20), setting the rotating speed of a vacuum stirrer to be 500r/min, and stirring at room temperature for 60min to prepare a mixed solution of the PVDF and the NMP; adding Carbon Nano Tubes (CNT) with a certain mass, and stirring for 60min to prepare a mixed solution of the CNT, PVDF and NMP; adding a certain mass of 5V anode material LiNi0.5Mn1.5O4(LNMO), stirring for 90min to prepare mixed slurry of LNMO, CNT, PVDF and NMP; respectively adding certain mass of conductive carbon black (SP) and conductive graphite (KS) and stirring for 60min to prepare the uniformly dispersed positive electrode material electrode slurry with the mass ratio of LNMO/CNT/SP/KS/PVDF being 80:0.3:4.85:4.85: 10.
Step two: the positive electrode material electrode slurry is subjected to preparation of a pole piece by the method of the step two in the step 1 (1) in the embodiment 2, so as to prepare the positive pole piece electrode of the high-voltage hybrid lithium ion supercapacitor.
(3) Preparation of LNMO/CNT/SP/KS/PVDF (80/5/2.5/2.5/10) pole piece
The method comprises the following steps: accurately weighing a certain mass of polyvinylidene fluoride (PVDF) powder, adding the PVDF powder into a vacuum stirring tank, and then adding the PVDF powder into the vacuum stirring tankAdding a certain mass of N-methylpyrrolidone (NMP) (the mass ratio of PVDF to NMP is 1: 20), setting the rotating speed of a vacuum stirrer to be 500r/min, and stirring at room temperature for 60min to prepare a mixed solution of PVDF and NMP; adding Carbon Nano Tubes (CNT) with a certain mass, and stirring for 60min to prepare a mixed solution of the CNT, PVDF and NMP; adding a certain mass of 5V anode material LiNi0.5Mn1.5O4(LNMO), stirring for 90min to prepare mixed slurry of LNMO, CNT, PVDF and NMP; respectively adding certain mass of conductive carbon black (SP) and conductive graphite (KS) and stirring for 60min to prepare the uniformly dispersed positive electrode material electrode slurry with the mass ratio of LNMO/CNT/SP/KS/PVDF being 80:5:2.5:2.5: 10.
Step two: the positive electrode material electrode slurry is subjected to preparation of a pole piece by the method of the step two in the step 1 (1) in the embodiment 2, so as to prepare the positive pole piece electrode of the high-voltage hybrid lithium ion supercapacitor.
2. Test of high-voltage hybrid lithium ion super capacitor positive plate
(1) High power Scanning Electron Microscope (SEM) testing
Performing characterization tests on the morphological characteristics of the positive plate electrode of the LNMO/SP/KS/PVDF (80/5/5/10), LNMO/CNT/SP/KS/PVDF (80/0.3/4.85/4.85/10) and LNMO/CNT/SP/KS/PVDF (80/5/2.5/2.5/10) by using a high-power Scanning Electron Microscope (SEM) (shown in figures 2, 3 and 4 respectively); the test result shows that: the conductive network in the CNT-free electrode is formed entirely by the agglomeration of conductive agent SP particles and the SP particle agglomerates have poor contact with the LNMO particles (fig. 2); a proper amount of CNT added into the composite electrode can be uniformly wound on the surface of LNMO particles and is connected with a conductive agent SP and conductive graphite KS to form a good conductive network together (figure 3); when the amount of CNT added to the composite electrode is excessive, the CNT is tightly coated on the surface of the LNMO particles (fig. 4), which will hinder the electrochemical activity.
(2) Packaging and testing of button half cells
The method comprises the following steps: package with a metal layer
The high voltage electrolyte prepared in example 1, the above positive plate electrode, and lithium plate, polypropylene/polyethylene composite porous film, LIR2025 battery case were packaged into a button type half cell in a glove box with controlled oxygen (< 1 ppm) and moisture (< 1 ppm).
Step two: testing
a. Cyclic voltammetry testing: enabling the half cell of the LNMO/CNT/SP/KS/PVDF (80/0.3/4.85/4.85/10) positive plate packaged in the step one to be in a voltage range of 2.80-4.95V and 0.1mVs-1The sweep rate of (a) was used to perform cyclic voltammetry tests (as shown in figure 5); the test result shows that: three pairs of oxidation-reduction peaks appear at 4.07V, 4.77V and 4.83V, which correspond to Mn of LNMO respectively3+/Mn4+、Ni2+/Ni3+、Ni3+/Ni4+The three redox processes of (a) indicate that LNMO has excellent electrochemical performance in the high voltage electrolyte.
b. And (3) multiplying power testing: and (3) carrying out constant-current charge and discharge test on the half cell packaged in the step one in a voltage range of 3.5-4.95V, wherein the test steps are set as follows: 0.5C charged, discharged at 0.5C, 1C, 3C, 5C, 8C, 10C, 15C, 20C, respectively (as shown in fig. 6); the test result shows that: the positive electrode sheet containing 0.3% CNT had a higher first 0.5C discharge capacity (0% CNT: 117 mAhg) than the positive electrode sheet containing 0% CNT and 5% CNT-1；0.3%CNT：125mAhg-1；5%CNT：93mAhg-1) And has a high 20C capacity retention ratio (0% CNT: 12.4 percent; 0.3% CNT: 75 percent; 5% of CNT: 1.3%), which shows that the rate capability of the LNMO can be greatly improved by performing composite modification on a certain amount of CNT and LNMO material to form a good conductive network (as shown in figure 3).
Example 3
The invention relates to a preparation method and a test method of a negative plate of a high-voltage hybrid lithium ion super capacitor.
1. Preparation of high-voltage mixed lithium ion super capacitor negative plate
(1) Preparation of AC/SP/SBR/CMC (90/5/3/2) Pole piece
The method comprises the following steps: accurately weighing a certain mass of sodium carboxymethylcellulose (CMC) powder, adding the CMC powder into a beaker, adding a certain mass of ultrapure water, putting a magneton with the length of 2cm, sealing the mouth of the beaker by using a plastic film and a rubber ring, placing the beaker on a magnetic stirrer, setting the rotating speed to be 100r/min, and stirring at room temperature for 12 hours to prepare a CMC aqueous solution with the mass fraction of 1%; accurately weighing a certain mass of 1% CMC aqueous solution, adding the 1% CMC aqueous solution into a vacuum stirring tank, then adding a certain mass of 50% Styrene Butadiene Rubber (SBR) aqueous solution, setting the rotating speed of a vacuum stirrer to be 500r/min, and stirring at room temperature for 30min to prepare a mixed solution of CMC and SBR; adding Activated Carbon (AC) powder with a certain mass, and stirring for 90min to obtain mixed slurry of AC, CMC and SBR; adding a certain mass of conductive carbon black (SP), and stirring for 60min to obtain the uniformly dispersed negative electrode material electrode slurry with the mass ratio of AC/SP/SBR/CMC being 90:5:3: 2.
Step two: vacuumizing and standing the cathode material electrode slurry for 10min, filtering by using a 100-mesh filter sieve, and coating the filtered cathode material electrode slurry on an aluminum foil current collector according to a certain thickness; and (3) drying the obtained pole piece at 60 ℃ for 3-6 h in vacuum, rolling according to a rolling ratio of 20%, slicing the rolled pole piece by using a slicing machine to obtain a circular pole piece with the diameter of 12mm, and drying at 60 ℃ for 10-12 h in vacuum to obtain the negative pole piece electrode of the high-voltage mixed lithium ion supercapacitor.
(2) Preparation of AC/CNT/SP/SBR/CMC (90/0.625/4.375/3/2) Pole pieces
The method comprises the following steps: accurately weighing a certain mass of sodium carboxymethylcellulose (CMC) powder, adding the CMC powder into a beaker, adding a certain mass of ultrapure water, putting a magneton with the length of 2cm, sealing the mouth of the beaker by using a plastic film and a rubber ring, placing the beaker on a magnetic stirrer, setting the rotating speed to be 100r/min, and stirring at room temperature for 12 hours to prepare a CMC aqueous solution with the mass fraction of 1%; accurately weighing a certain mass of 1% CMC aqueous solution, adding into a vacuum stirring tank, then adding a certain mass of 50% Styrene Butadiene Rubber (SBR) aqueous solution, setting the rotating speed of the vacuum stirrer to be 500r/min, and stirring at room temperature for 30min to prepare a mixed solution of CMC and SBR; adding Carbon Nano Tube (CNT) with a certain mass, and stirring for 30min to obtain a mixed solution of CNT, CMC and SBR; adding Activated Carbon (AC) powder with a certain mass, and stirring for 90min to obtain mixed slurry of AC, CNT, CMC and SBR; adding a certain mass of conductive carbon black (SP), and stirring for 60min to obtain the uniformly dispersed negative electrode material electrode slurry with the mass part ratio of AC/CNT/SP/SBR/CMC being 90:0.625:4.375:3: 2.
Step two: and (2) preparing a pole piece from the negative electrode material electrode slurry according to the method of the step (1) and the step (II) in the embodiment 3 to prepare a negative pole piece electrode of the high-voltage hybrid lithium ion supercapacitor.
(3) Preparation of AC/CNT/SBR/CMC (90/5/3/2) Pole piece
The method comprises the following steps: accurately weighing a certain mass of sodium carboxymethylcellulose (CMC) powder, adding the CMC powder into a beaker, adding a certain mass of ultrapure water, putting a magneton with the length of 2cm, sealing the mouth of the beaker by using a plastic film and a rubber ring, placing the beaker on a magnetic stirrer, setting the rotating speed to be 100r/min, and stirring at room temperature for 12 hours to prepare a CMC aqueous solution with the mass fraction of 1%; accurately weighing a certain mass of 1% CMC aqueous solution, adding into a vacuum stirring tank, then adding a certain mass of 50% Styrene Butadiene Rubber (SBR) aqueous solution, setting the rotating speed of the vacuum stirrer to be 500r/min, and stirring at room temperature for 30min to prepare a mixed solution of CMC and SBR; adding Carbon Nano Tube (CNT) with a certain mass, and stirring for 30min to obtain a mixed solution of CNT, CMC and SBR; adding a certain mass of Activated Carbon (AC) powder, and stirring for 90min to prepare the uniformly dispersed negative electrode material electrode slurry with the mass ratio of AC/CNT/SBR/CMC being 90:5:3: 2.
Step two: the negative electrode material electrode slurry is subjected to preparation of a pole piece according to the method of the step two in the step 1 (1) in the embodiment 3, so that a negative pole piece electrode of the high-voltage hybrid lithium ion supercapacitor is prepared.
2. Test of high-voltage hybrid lithium ion supercapacitor negative plate
(1) High power Scanning Electron Microscope (SEM) testing
Performing characterization tests on the morphology characteristics of the AC/SP/SBR/CMC (90/5/3/2), AC/CNT/SP/SBR/CMC (90/0.625/4.375/3/2) and AC/CNT/SBR/CMC (90/5/3/2) negative plate electrodes by using a high-power Scanning Electron Microscope (SEM) (shown in figures 7, 8 and 9 respectively); the test result shows that: the conductive network in the CNT-free electrode is formed entirely by the agglomeration of conductive agent SP particles, and the contact between SP particle agglomerates and AC particles is poor (fig. 7); an appropriate amount of CNTs added to the composite electrode can be uniformly wound on the surface of the AC particles and connected with the conductive agent SP to form a good conductive network (fig. 8); when the amount of CNT added to the composite electrode is excessive, the CNT is tightly coated on the surface of the AC particle (fig. 9), which will hinder the electrochemical activity.
(2) Packaging and testing of button half cells
The method comprises the following steps: package with a metal layer
The high-voltage electrolyte prepared in example 1, the negative electrode plate electrode, the lithium plate, the polypropylene/polyethylene composite porous film and the LIR2025 battery case were packaged into a button type half cell in a glove box with controlled oxygen (< 1 ppm) and moisture (< 1 ppm).
Step two: testing
a. Cyclic voltammetry testing: the half cell of the AC/CNT/SP/SBR/CMC (90/0.625/4.375/3/2) negative plate packaged in the first step is controlled to be within the voltage range of 1.3-3.6V and 5mVs-1Cyclic voltammetry test (as shown in fig. 10) was performed at the scan rate of (a); the test result shows that: the AC presents an obvious rectangular cyclic voltammetry curve in a voltage range of 1.3-3.6V, which shows that the AC has excellent double electric layer capacitance characteristics in a wider voltage range of the high-voltage electrolyte.
b. And (3) rate testing: and C, performing constant-current charge and discharge test on the half cell packaged in the step one in a voltage range of 1.5-3.0V, and respectively setting current densities as follows: 0.015Ag-1、0.03Ag-1、0.06Ag-1、0.12Ag-1、0.24Ag-1、0.48Ag-1、0.96Ag-1、1.92Ag-1(as shown in FIG. 11); the test result shows that: the negative electrode sheet containing 0.625% CNT had a higher 1.92Ag than the negative electrode sheet containing 0% CNT and 5% CNT-1The capacity retention rate (0% CNT: 28.4%, 0.625% CNT: 38.6%, 5% CNT: 21.9%) shows that the rate capability of AC can be greatly improved by performing composite modification on a certain amount of CNT and AC material to form a good conductive network (as shown in figure 8).
Example 4
The invention relates to packaging and testing of a high-voltage hybrid lithium ion supercapacitor.
The method comprises the following steps: package with a metal layer
The high voltage electrolyte prepared in example 1, the positive electrode plate electrode of LNMO/CNT/SP/KS/PVDF (80/0.3/4.85/4.85/10) prepared in example 2, the negative electrode plate electrode of AC/CNT/SP/SBR/CMC (90/0.625/4.375/3/2) prepared in example 3, and the polypropylene/polyethylene composite porous film, LIR2025 battery case were packaged into a button capacitor in a glove box with controlled oxygen (< 1 ppm) and moisture (< 1 ppm). Wherein the ratio of the positive electrode capacity to the negative electrode capacity is 3.5: 1.
Step two: testing
a. Cyclic voltammetry testing: the voltage of the button capacitor packaged in the first step is within the range of 0-3.5V and 1mVs-1Cyclic voltammetry measurements were performed at the scan rate of (c) (as shown in fig. 12); the test result shows that: the hybrid lithium ion supercapacitor prepared by packaging the high-voltage electrolyte, the nano-carbon composite modified LNMO positive electrode and the nano-carbon composite modified AC negative electrode has a higher working voltage (up to 3.5V), and the cyclic voltammetry characteristic (figure 12) is the combination of the cyclic voltammetry characteristics of the positive electrode (figure 5) and the negative electrode (figure 10) which form the capacitor; the obtained hybrid lithium ion super capacitor well maintains the oxidation-reduction electrochemical performance of the battery anode and the electric double layer capacitance characteristic of the capacitor cathode, so that the hybrid lithium ion super capacitor has higher power density than a lithium ion battery and higher energy density than an electric double layer capacitor.
b. And (3) rate testing: and C, performing constant-current charge and discharge test on the button capacitor packaged in the step I within the voltage range of 0-3.45V, and respectively setting the current density as follows: 0.015Ag-1、0.03Ag-1、0.06Ag-1、0.12Ag-1、0.24Ag-1、0.48Ag-1、0.96Ag-1、1.92Ag-1、2Ag-1、4Ag-1、6Ag-1、8Ag-1、10Ag-1、12Ag-1、15Ag-1、20Ag-1、22Ag-1、24Ag-1、26Ag-1、28Ag-1(as shown in FIG. 17); the test result shows that: the mixed lithium ion superThe stage capacitor has higher maximum energy density (56 Whkg)-1) And maximum power density (21 kWkg)-1）。
c. And (3) testing the cycle life: performing constant-current charge-discharge cycle test on the button capacitor packaged in the step one in a voltage range of 0-3.45V, and setting the current density to be 5C (as shown in figure 13); the test result shows that: in the charge-discharge cycle process, the hybrid lithium ion super capacitor has higher coulombic efficiency (100%); after 4500 cycles, a high capacity retention rate (98%) was still maintained.
The LNMO/CNT/SP/KS/PVDF (80/0.3/4.85/4.85/10) positive plate electrodes with different thicknesses prepared in example 2 and the AC/CNT/SP/SBR/CMC (90/0.625/4.375/3/2) negative plate electrodes with different thicknesses prepared in example 3 are selected according to different positive electrode-negative electrode capacity ratios, and the button type hybrid lithium ion super capacitor is packaged and tested according to the method. The results are shown in Table 1.
TABLE 1 Performance of high voltage hybrid lithium ion supercapacitor tested at 0-3.45V
Comparative example 1
And (3) preparing and testing electrodes (positive plates/negative plates) of the conventional symmetrical double-electric-layer super capacitor and the capacitor.
(1) Preparation of AC/SP/SBR/CMC (90/5/3/2) Pole piece
The method comprises the following steps: accurately weighing a certain mass of sodium carboxymethylcellulose (CMC) powder, adding the CMC powder into a beaker, adding a certain mass of ultrapure water, putting a magneton with the length of 2cm, sealing the mouth of the beaker by using a plastic film and a rubber ring, placing the beaker on a magnetic stirrer, setting the rotating speed to be 100r/min, and stirring at room temperature for 12 hours to prepare a CMC aqueous solution with the mass fraction of 1%; accurately weighing a certain mass of 1% CMC aqueous solution, adding the 1% CMC aqueous solution into a vacuum stirring tank, then adding a certain mass of 50% SBR aqueous solution, setting the rotating speed of a vacuum stirrer to be 500r/min, and stirring for 30min at room temperature to prepare a mixed solution of CMC and SBR; adding Activated Carbon (AC) powder with a certain mass, and stirring for 90min to obtain mixed slurry of AC, CMC and SBR; adding a certain mass of conductive carbon black (SP), and stirring for 60min to obtain the uniformly dispersed electrode slurry with the mass part ratio of AC/SP/SBR/CMC being 90:5:3: 2.
Step two: vacuumizing and standing the electrode slurry for 10min, filtering the electrode slurry by using a 100-mesh filter screen, and coating the electrode slurry on an aluminum foil current collector according to a certain thickness; and (3) drying the obtained pole piece at 60 ℃ in vacuum for 3-6 h, rolling according to a rolling ratio of 20%, slicing the rolled pole piece by using a slicing machine to obtain a circular pole piece with the diameter of 12mm, and drying at 60 ℃ in vacuum for 10-12 h to obtain the electrode (positive plate/negative plate) of the conventional symmetrical double-electric-layer supercapacitor.
Step three: carrying out characterization test on the morphology characteristics of the electrode pole piece by using a high-power Scanning Electron Microscope (SEM) (as shown in figure 14); the test result shows that: the conductive network in the resulting electrode is formed entirely by the agglomeration of the conductive agent SP particles, and the SP particle agglomerates have poor contact with the AC particles.
(2) Packaging and testing of conventional symmetric double electric layer super capacitor
The method comprises the following steps: package with a metal layer
In the control of oxygen (<1 ppm) and water (<1 ppm), the above-mentioned electrodes (positive electrode plate/negative electrode plate), and 1mol L-1[TEA][BF4]The button capacitor is packaged by the aid of the/ACN electrolyte, the cellulose acetate diaphragm and the LIR2025 battery shell; wherein the capacity ratio of the anode to the cathode is 1: 1.
Step two: testing of
a. Cyclic voltammetry test: the voltage of the button capacitor packaged in the first step is within the range of 0-2.7V and 5mVs-1Cyclic voltammetry measurements were performed at the scan rate of (c) (as shown in fig. 15); the test result shows that: the capacitor exhibited a pronounced rectangular cyclic voltammogram, indicating its typical double layer capacitance characteristics.
b. And (3) rate testing: performing constant-current charge and discharge test on the button capacitor packaged in the step one in a voltage range of 0-2.7V to obtain currentThe density was set as: 0.5Ag-1、1Ag-1、2Ag-1、4Ag-1、8Ag-1、10Ag-1、15Ag-1、20Ag-1、30Ag-1(as shown in FIG. 17); the test result shows that: the maximum energy density and the maximum power density of the conventional symmetrical double electric layer super capacitor are respectively 25Whkg-1And 32kWkg-1。
c. And (3) testing the cycle life: performing constant-current charge-discharge cycle test on the button capacitor packaged in the step one in a voltage range of 0-2.7V, and setting the current density to be 10Ag-1(as shown in FIG. 16); the test result shows that: after 4500 cycles, the conventional symmetrical double-layer supercapacitor has reasonable coulombic efficiency (94%) and capacity retention rate (91%).
Comparative analysis
According to the invention, the nano carbon material is introduced to respectively carry out composite modification on the 5V anode material and the porous carbon material. In the obtained nano composite electrode material, the nano carbon material is uniformly wound (coated) on the surface of the 5V positive electrode material or porous carbon material particles, and is connected with the conductive agent particles to form a good conductive network (attached figures 3 and 8). Compared with the conventional electrode materials (attached figures 2 and 7) which are not compounded by the nano carbon material, the nano carbon material compounding modification technology can improve the conductivity and rate capability of the 5V positive electrode material and the porous carbon negative electrode material (attached figures 6 and 11), so that the power characteristic, the safety and the cycle service life of the obtained hybrid lithium ion super capacitor are improved.
According to the invention, the 5V positive electrode material anode compositely modified by the nano carbon material and the porous carbon material cathode are combined, so that the prepared hybrid lithium ion super capacitor well maintains the redox electrochemical performance of the battery anode (shown in figure 5) and the electric double layer capacitance characteristic of the capacitor cathode (shown in figure 10), and therefore, the hybrid lithium ion super capacitor has higher power density than a lithium ion battery and higher energy density than an electric double layer capacitor. By optimizing the capacity ratio of the positive electrode and the negative electrode, the charging and discharging processes can be better matched, so that the working voltage (figure 12) of the obtained hybrid lithium ion super capacitor is obviously improved compared with the conventional symmetrical double electric layer super capacitor (figure 15), and further, the energy density and the power density (figure 17) of the hybrid lithium ion super capacitor are obviously improved.
According to the invention, the organic solvent suitable for the high-voltage electrolyte, the lithium salt electrolyte suitable for the high-voltage electrolyte and the electrolyte additive capable of stabilizing the high-voltage anode material are selected, so that the obtained high-voltage electrolyte has a wider safe electrochemical window, and the additive can be oxidized on the surface of an electrode to form an effective protective film (figure 1), so that the obtained hybrid lithium ion super capacitor has higher working voltage, better safety and cycle service life (figure 13).
In conclusion, the high-voltage hybrid lithium-ion supercapacitor provided by the invention has the advantages of higher working voltage, energy density, power density, safety and cycle service life.
Claims (8)
1. The utility model provides a high voltage hybrid lithium ion ultracapacitor system, ultracapacitor system includes positive plate, negative pole piece, the diaphragm between positive negative pole, fills electrolyte, the casing in positive negative pole and diaphragm space, its characterized in that: selecting an organic solvent suitable for a high-voltage electrolyte, a lithium salt electrolyte suitable for the high-voltage electrolyte and an electrolyte additive capable of stabilizing a high-voltage positive electrode material, and preparing the high-voltage electrolyte suitable for a high-voltage hybrid lithium ion supercapacitor; the capacitor is packaged by a 5V anode material anode and a porous carbon material cathode which are compositely modified by a nano carbon material and a high-voltage electrolyte, and the capacity ratio of the anode and the cathode is optimized, so that the charge and discharge processes of the anode and the cathode can be better matched, the working voltage of the capacitor is improved and stabilized to be more than 3.4V, and the capacitor is used for a high-energy density/high-power density super capacitor and has the advantages of high power characteristic, high safety and long cycle service life;
the positive plate and/or the negative plate consists of a current collector and an electrode material coated on the surface of the current collector and comprising a nano carbon material, and the electrolyte is a high-voltage electrolyte formed by mixing an organic solvent, a lithium salt and an additive;
the electrode material of the positive plate consists of 50-97.99% of 5V positive material, 0.01-10% of nano carbon material, 1-50% of conductive agent and 1-50% of binder in percentage by mass; the 5V positive electrode material is spinel type LiMxMn material2-xO4Olivine-type material LiNPO4Lithium-rich manganese-based material xLi with layered structure2MnO3•（1-x）LiYO2At least one of, wherein: 0 < x <1, M = Fe, Cu, Co, Ni, Cr, N = Mn, Co, Ni, Cr, Y = Mn, Co, Ni; the electrode material of the positive electrode sheet comprises LNMO, CNT, SP, KS, PVDF, and the weight ratio of the LNMO to the CNT is 80:0.3:4.85:4.85: 10;
the electrode material of the negative plate consists of 50-97.99% of porous carbon material, 0.01-10% of nano carbon material, 1-50% of conductive agent and 1-50% of binder by mass percentage; the nano carbon material is at least one of carbon nano tube, carbon nano fiber and graphene; the carbon nano tube is a single-walled carbon nano tube and/or a multi-walled carbon nano tube, and the graphene is single-layer graphene and/or multi-layer graphene; the conductive agent is conductive graphite and conductive carbon black; the binder is polyvinylidene fluoride;
the electrolyte is a high-voltage electrolyte formed by mixing an organic solvent, lithium salt and an additive, wherein the organic solvent consists of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate in a volume ratio of 1:1: 1; the lithium salt is LiClO4、LiPF6、LiBOB、LiBF4、LiODFB、LiTFSI、LiFSI、LiPO2F2At least one of LiODFP; the additive is TPPi, LiBOB, LiODFB, LiBMB, LiBSO4F2At least one of PTS and TMB.
2. The high-voltage hybrid lithium-ion supercapacitor according to claim 1, wherein the ratio of the positive electrode capacity to the negative electrode capacity of the high-voltage hybrid lithium-ion supercapacitor is 1: 1-10: 1, the high-voltage hybrid lithium-ion supercapacitor is packaged in any one of a button type, a cylindrical type, a square type and a special shape, and the high-voltage hybrid lithium-ion supercapacitor is packaged in any one of a steel shell, a plastic shell, an aluminum shell and an aluminum-plastic film.
3. The high-voltage hybrid lithium-ion supercapacitor according to claim 1, wherein the concentration of lithium salt in the high-voltage electrolyte is 0.1 to 10mol L-1(ii) a The content of the additive is 0.01-10% by mass.
4. The high-voltage hybrid lithium ion supercapacitor according to claim 1 or 3, wherein the lithium salt in the high-voltage electrolyte is LiPF6The additive is TPPi; the high-voltage electrolyte is prepared by mixing and stirring ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate uniformly to obtain a required mixed solvent, and accurately weighing LiPF with a certain mass6Adding TPPi and TPPi into the obtained mixed solvent, dissolving, stirring, adding a certain amount of molecular sieve, standing for 24 hr to obtain a solution containing 1mol L-1LiPF60.2% TPPi.
5. A preparation method of the high-voltage hybrid lithium ion supercapacitor according to any one of claims 1 to 4, characterized in that the supercapacitor is prepared by the steps of high-voltage electrolyte preparation, positive plate preparation, negative plate preparation and packaging:
A. preparing a high-voltage electrolyte: under the inert gas atmosphere condition that oxygen is controlled to be less than 1ppm and moisture is controlled to be less than 1ppm, uniformly mixing selected organic solvent, lithium salt and additive according to a certain mass ratio to prepare high-voltage electrolyte;
B. preparing a positive plate: adding a 5V positive electrode material, a nano carbon material, a conductive agent and a binder into N-methyl pyrrolidone according to a certain mass ratio, stirring at a high speed in vacuum to form positive electrode slurry, uniformly coating the positive electrode slurry on the surface of a current collector, and drying, rolling and cutting to obtain a positive electrode sheet;
C. preparing a negative plate: adding a porous carbon material, a nano carbon material, a conductive agent and a binder into deionized water according to a certain mass ratio, stirring at a high speed in vacuum to form negative electrode slurry, then uniformly coating the negative electrode slurry on the surface of a current collector, and drying, rolling and cutting to obtain a negative electrode sheet;
D. packaging: and packaging the high-voltage electrolyte, the positive plate, the negative plate and the diaphragm under the inert gas atmosphere condition of controlling oxygen to be less than 1ppm and moisture to be less than 1ppm to obtain the high-voltage hybrid lithium ion supercapacitor.
6. The method for preparing a high-voltage hybrid lithium ion supercapacitor according to claim 5, wherein the concentration of lithium salt in the high-voltage electrolyte prepared in the step A is 0.1-10 mol L-1And/or the content of the additive is 0.01-10% by mass.
7. The method for preparing a high-voltage hybrid lithium-ion supercapacitor according to claim 5, wherein the content of each substance in the step B is as follows by mass percent: 50-97.99% of 5V positive electrode material, 0.01-10% of nano carbon material, 1-50% of conductive agent and 1-50% of binder.
8. The method for preparing a high-voltage hybrid lithium-ion supercapacitor according to claim 5, wherein the content of each substance in the step C is as follows by mass percent: 50-97.99% of porous carbon material, 0.01-10% of nano carbon material, 1-50% of conductive agent and 1-50% of binder.
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| CN105336504A (en) * | 2015-09-24 | 2016-02-17 | 宁波南车新能源科技有限公司 | Hybrid capacitor battery |
| CN105551816A (en) * | 2015-12-21 | 2016-05-04 | 中航锂电（洛阳）有限公司 | Positive plate of hybrid super capacitor and preparation method of positive plate and hybrid super capacitor |
| CN107834061A (en) * | 2017-11-17 | 2018-03-23 | 中国科学院青岛生物能源与过程研究所 | A kind of method of modifying for improving lithium-rich manganese base material chemical property |
| CN108649265A (en) * | 2018-05-10 | 2018-10-12 | 桑德集团有限公司 | Electrolysis additive, lithium battery electrolytes and lithium battery |
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| Publication number | Publication date |
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| CN114743803B (en) | 2023-12-29 |
| CN109378220A (en) | 2019-02-22 |
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