CN111696792B - Organic nanometer negative electrode based on insertion layer type pseudo-capacitor and preparation method and application thereof - Google Patents

Organic nanometer negative electrode based on insertion layer type pseudo-capacitor and preparation method and application thereof Download PDF

Info

Publication number
CN111696792B
CN111696792B CN202010613224.5A CN202010613224A CN111696792B CN 111696792 B CN111696792 B CN 111696792B CN 202010613224 A CN202010613224 A CN 202010613224A CN 111696792 B CN111696792 B CN 111696792B
Authority
CN
China
Prior art keywords
organic
pseudocapacitance
negative electrode
layer type
insertion layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010613224.5A
Other languages
Chinese (zh)
Other versions
CN111696792A (en
Inventor
张力
刘建军
胡忠利
赵晓琳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN202010613224.5A priority Critical patent/CN111696792B/en
Publication of CN111696792A publication Critical patent/CN111696792A/en
Application granted granted Critical
Publication of CN111696792B publication Critical patent/CN111696792B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Nanotechnology (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses an organic nanometer negative electrode based on an insertion layer type pseudocapacitance, which comprises an active material, a conductive agent and a binder, wherein the active material is an organic molecular crystal material. The invention uses the nano organic molecular crystal material as the cathode material of the lithium ion battery or the lithium ion hybrid capacitor, and the like, so that the organic nano crystal can be fully contacted with the conductive agent in the electrode, has good electronic conductivity, and can remarkably improve the reversible capacity of the lithium ion battery and the energy density of the lithium ion hybrid capacitor.

Description

Organic nanometer negative electrode based on insertion layer type pseudo-capacitor and preparation method and application thereof
Technical Field
The invention belongs to the field of energy devices, relates to an organic nano negative electrode, and particularly relates to a nano organic negative electrode with ultrahigh intercalation type pseudocapacitance lithium ion storage specific capacity, and a preparation method and application thereof.
Background
Currently, electrochemical energy storage devices, such as lithium ion batteries and supercapacitors, have been widely used in people's daily life and transportation, and have also triggered further pursuits of high energy density/power density. The lithium ion battery is a system with higher energy density in the currently practical battery, but the power density is relatively lower; in contrast, supercapacitors have excellent power density and cycle life, but there are severe shortboards in energy density. The performance difference is mainly determined by the difference of the two working mechanisms.
In order to overcome the disadvantages of the above systems in terms of energy and power density, a novel electrochemical energy storage device has been proposed in recent years, in which a capacitive positive electrode material and a battery-type negative electrode material are integrated into a system to construct lithium-ion hybrid capacitors (LICs). The lithium-ion hybrid capacitor effectively combines the advantages of a lithium-ion battery and a super capacitor, and therefore has high energy density, long endurance and fast storage/discharge speed. Lithium ion hybrid capacitor when charging, Li+Ions are embedded into a battery type negative electrode material through electrolyte under the action of an external electric field to generate a Faraday reaction; meanwhile, anions are adsorbed to the surface of the capacitance type anode in a non-Faraday reaction, and meanwhile, equal amount of electrons flow from the anode to the cathode through an external circuit; upon discharge, Li+Ions are released from the battery type negative electrode, meanwhile, anions are desorbed from the capacitance type positive electrode, and electrons in an external circuit flow from the negative electrode to the positive electrode to form current, so that energy output is realized.
In 2001, Amatucci et al used LiPF for the first time6Acetonitrile as electrolyte, respectively AC (activated carbon) and lithium titanium oxide (such as Li)4Ti5O12) Lithium ion hybrid capacitors were assembled as the positive and negative electrode materials. Research shows that the system can keep 90% of capacity under low multiplying power under the condition of high charging/discharging multiplying power of 10C, and the capacity retention rate can reach 85-90% after 500 cycles. Therefore, the lithium ion hybrid capacitor has good rate performance and cycling stability, and the service life is considerable, which is the first report about the lithium ion hybrid capacitor. Thereafter, Hatozaki of fuji co, japan used activated carbon as a positive electrode material and pre-intercalated lithium graphite or the like as a negative electrode material to prepare a hybrid capacitor, and was formally named a lithium-ion hybrid capacitor. Subsequently, the lithium ion hybrid capacitor has undergone a vigorous development process, and various lithium ion hybrid capacitors having excellent properties have been developed so far.
Negative electrodes of the cell type due to electrochemical hysteresisTend to be the primary reason for limiting the output power and high energy density of lithium ion hybrid capacitors. In contrast to the surface-controlled charge storage of positive porous electrodes (typically high specific surface active carbon, graphene and carbon nanotubes and other carbon-based materials), negative electrodes are primarily limited by the inherent semi-infinite diffusion process within the bulk of the electrode material. Therefore, research on lithium-ion hybrid capacitors has been focused on battery-type negative electrode materials, mainly including carbon-based materials and lithium intercalation compounds (Li)4Ti5O12、Nb2O5Etc.), alloying materials, conversion materials, etc. F.B Reguin et al used commercial graphite as the negative electrode and commercial activated carbon as the positive electrode, with 1M LiPF6DMC (1: 1) as electrolyte, assembling a lithium-ion hybrid capacitor. Under a wide voltage window of 1.5-5.0V, the maximum energy density and the maximum power density of the device can respectively reach 145.8Wh kg-1And 10kW kg-1(ii) a However, under the voltage window, the attenuation of the capacitor is obvious, and the capacity retention rate is 60% after 10000 circles. The Xiahui of Nanjing university of rational and the remnants of Chinese science and technology university, etc. take commercial bacterial cellulose membrane as initial material to prepare a boron-nitrogen double-doped three-dimensional porous carbon nanofiber network structure (BNC); and the BNC is successfully used for the high-performance BNC// BNC lithium ion capacitor. The results show that the power density is 225W kg-1The symmetric double-carbon lithium ion capacitor is 220Wh kg-1High energy density of (2); and 104Wh kg at the energy density-1Then the power density of the LICs can reach 22500W kg-1The performance of the compound is far better than that of the reported LICs. Lucun peak and hero et al, the university of harbin industry, reported a lithium ion capacitor assembled from high concentration nitrogen doped carbon nanospheres (ANCS). The nitrogen doping optimizes the stacking parameters of the carbon microcrystal structure, improves the active points of the carbon material, and further improves the Li content of the anode and cathode materials+And PF6 -The storage capacity of (2). The ANCS and the pre-lithiated ANCS are combined to obtain the all-carbon mixed ion capacitor with the potential window reaching 4.5V, the all-carbon mixed ion capacitor has extremely excellent electrochemical performance, and the maximum energy density can reach 206.7Wh kg-1The maximum power density can reach 22.5kW kg-1(ii) a It is high powerThe rate cycling stability is especially outstanding, and can be 4A g -110000 cycles of current density, the capacity loss per cycle is only 0.00134%.
Compared with carbon material negative electrodes, alloying materials, conversion materials and other embedded bulk materials generally have the common problems of poor electronic conductivity, slow reaction kinetics, poor electrochemical performance and the like. For these types of negative electrode materials, people usually adopt nanocrystallization technology and carbon coating technology to improve their electrochemical properties. Preparing nitrogen-doped carbon-coated Co by pyrolyzing a bimetallic organic framework (ZnCo-ZIF) step by step in Nanjing university gold bell and the like3ZnC nano polyhedral particle (Co)3ZnC @ NC) serving as a negative electrode material is combined with a microporous carbon (MPC) positive electrode material with high specific surface area derived from biomass pine needles to obtain the lithium ion hybrid capacitor with high energy density. Within the working voltage range of 1.0-4.5V, the lithium ion hybrid capacitor is 275W kg-1The energy density is up to 141.4Wh kg-1And at 15.2Wh kg-1The power density of the energy can reach 10.3kW kg-1. The LTO/graphene composite material is prepared by combining an atomic layer deposition breeding technology with subsequent heat treatment lithiation, such as Wangchun university of Hebei industry. The lithium ion mixed capacitor is assembled by matching with an active carbon anode material, and the maximum energy density of the lithium ion mixed capacitor is 52Wh kg-1The maximum power density can reach 57.6kW kg-1And at 25A g-1The capacity retention rate is up to 97% after 2000 cycles under the current density.
At present, the lithium ion hybrid capacitor cathode material is mainly concentrated on inorganic metal oxide/nitride and other materials, and is restricted by the problems of theoretical specific capacity, oxidation-reduction potential, insufficient metal mineral deposit, great environmental pollution and the like, so that the green and high-energy requirements of next-generation pure energy devices are difficult to meet. Compared with the traditional inorganic material, the organic material has the advantages of low price, environmental protection, high theoretical specific capacity and the like. More importantly, the organic material has the advantages of variety diversity, designability of structure, adjustable oxidation-reduction potential and the like, and can provide rich choices for selecting the cathode of the lithium-ion hybrid capacitor, so that the organic material has wide research and development and application prospects. However, the application of organic materials to the negative electrode of lithium ion hybrid capacitors has been recently reported. This is mainly due to three reasons: the organic material has electronic insulation property, is easy to dissolve in an organic solvent and has defects in a synthetic method for preparing the organic nano material.
In conclusion, the development of high-performance organic nano-electrode materials as negative electrode materials of lithium ion hybrid capacitors is a key supporting technology for developing next generation of high-performance green sustainable lithium ion batteries/hybrid capacitors.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nano organic negative electrode with ultrahigh insertion layer type pseudocapacitance lithium ion storage specific capacity.
The invention provides an organic nanometer negative electrode based on an insertion layer type pseudocapacitance, which comprises an active material, a conductive agent and a binder, wherein the active material is an organic molecular crystal material, the crystal structure of the organic molecular crystal material is a hexagonal or monoclinic layered structure, and the interlayer distance is 0.2-0.6 nm.
Further, the organic molecular crystal material is a mixture of one or more selected from 2,2 '-bipyridyl-4, 4' -dicarboxylic acid, fumaric acid, sodium citrate, cyclohexadecanone, organic conjugated small molecular carboxylic acid, organic small molecular carboxylic acid lithium salt, organic small molecular carboxylic acid sodium salt, organic small molecular carboxylic acid potassium salt, organic conjugated acid anhydride, organic conjugated quinones, organic conjugated sulfur, organic conjugated azobenzene and organic conductive polymers.
Still further, the organic molecular crystal material is a mixture of one or more selected from the group consisting of 2,2' -bipyridine-3, 3' -dicarboxylic acid, 2' -bipyridine-5, 5' -dicarboxylic acid, maleic acid, itaconic acid, terephthalic acid, naphthalene tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, dilithium rhodizonate, tetralithium rhodizonate, hexalithium rhodizonate, sodium rhodizonate, lithium terephthalate, lithium 2, 4-dienyl adipate, azobenzene, sodium 4- (phenylazo) benzoate, sodium azobenzene-4, 4' -dicarboxylate, polydopamine, and polymer PQL.
Optimally, the mass ratio of the active material to the conductive agent to the binder is 5-8: 1-4: 1.
Preferably, the binder is a mixture of one or more of polyvinylidene fluoride, carboxymethyl cellulose, sodium alginate, LA132, lignocellulose and polytetrafluoroethylene.
The invention also aims to provide a preparation method of the organic nanometer negative electrode based on the insertion layer type pseudocapacitance, which comprises the following steps:
(a) mixing the active material, the conductive agent and the binder, adding a solvent, and performing ball milling to obtain viscous slurry;
(b) coating the viscous slurry on a metal foil, and drying to obtain a pole piece;
(c) and rolling and punching the pole piece.
Preferably, in the step (a), the solvent is a mixture of one or more selected from the group consisting of N-methylpyrrolidone, water and ethanol.
The invention further aims to provide application of the organic nanometer negative electrode based on the insertion layer type pseudocapacitance, which is used for assembling a lithium ion hybrid capacitor with a positive electrode and an electrolyte.
Optimally, the active material of the positive electrode is commercial porous activated carbon, S-doped porous carbon, N-doped porous carbon, P-doped porous carbon, biomass-derived porous activated carbon or metal organic framework-derived porous carbon.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the invention uses the nano organic molecular crystal material as the cathode material of the lithium ion battery or the lithium ion hybrid capacitor, and the like, so that the organic nano crystal can be fully contacted with the conductive agent in the electrode, has good electronic conductivity, and can remarkably improve the reversible capacity of the lithium ion battery and the energy density of the lithium ion hybrid capacitor. As exemplified by 2,2 '-bipyridine-4, 4' -dicarboxylic acid: 2,2 '-bipyridine-4, 4' -dicarboxylic acid has an-OH, -C ═ O, and-C ═ N group in the molecular structure, and during the first discharge, the-OH group undergoes an irreversible lithiation reaction first, followed by redox reactions of the-C ═ O and-C ═ N functional groups. Compared with the conventional carbonyl compound, the 2,2 '-bipyridine-4, 4' -dicarboxylic acid has two reversible electroactive functional groups and a lower molecular weight, and thus has a higher reversible capacity.
(2) The crystal structure of the selected nano organic molecular crystal is a hexagonal or monoclinic layered structure, and the interlayer distance is 0.2-0.6 nm, so that the layered structure is very favorable for lithium ions to be embedded into the layers of the molecular crystal at high speed without being influenced by diffusion control, and the ultrahigh intercalation pseudocapacitance capacity is obtained. Continuing with the nanocrystal structure of 2,2 '-bipyridine-4, 4' -dicarboxylic acid as an example: lithium ions are rapidly inserted into an intercrystalline channel of 2,2 '-bipyridine-4, 4' -dicarboxylic acid during charging; during discharging, the lithium ions entering the molecular crystal layers can return to the electrolyte again, and the stored charges are released through an external circuit. The process of charge/discharge is a reversible process of intercalation and deintercalation of lithium ions between molecular crystal layers; the 2,2 '-bipyridine-4, 4' -dicarboxylic acid molecular crystal has larger interlayer spacing, so that lithium ions can be more favorably and rapidly inserted and removed between the layers, and the lithium ion hybrid capacitor has higher energy density and power density;
(3) the nanometer organic molecular crystal with proper crystal face and space is used as the cathode active material of the lithium ion battery and the lithium ion hybrid capacitor, and the nanometer organic molecular crystal generally has lower oxidation-reduction potential, so that the working voltage window of the lithium ion hybrid capacitor can be obviously improved.
(4) The nano organic molecular crystal generally has excellent anti-dissolving capacity in ester and ether electrolytes, does not dissolve in the circulating process, and can be used for preparing a stable negative pole piece.
(5) The nano organic molecular crystal generally has insulating property, but the nano organic molecular crystal is beneficial to fully combining with a conductive network formed by a binder and a conductive agent, so that the overall conductivity of an electrode cannot be reduced when the nano organic molecular crystal is used as a negative electrode material, and the rate performance cannot be influenced.
(6) The nano organic molecular crystals generally have a higher melting point. For example, the melting point of 2,2 '-bipyridyl-4, 4' -dicarboxylic acid is as high as 310 ℃, which is obviously higher than that of electrolytic solution solvents such as DEC, DMC and EMC, and the like, and when the lithium ion battery cathode can be used as a cathode, the safety of lithium ion batteries and lithium ion hybrid capacitors can be effectively ensured.
(7) The lithium ion battery and the lithium ion hybrid capacitor based on the nano organic molecular crystal cathode have high energy density, excellent power characteristics and excellent cycle performance, and the electrochemical performance of the lithium ion battery and the lithium ion hybrid capacitor is remarkably superior to that of the existing lithium ion hybrid capacitor at present;
(8) the invention initiates a preparation method of the nano organic molecular crystal, namely a dissolving and drying recrystallization process based on high-energy ball milling, and has simple process and low cost.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a 2,2 '-bipyridine-4, 4' -dicarboxylic acid-based electrode sheet prepared in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) image of a pole piece based on 2,2 '-bipyridine-4, 4' -dicarboxylic acid prepared in example 1;
FIG. 3 is a graph of the rate performance of a lithium-ion battery cell based on 2,2 '-bipyridine-4, 4' -dicarboxylic acid prepared in example 1;
FIG. 4 is a graph of the cycle performance of a lithium ion battery based on 2,2 '-bipyridine-4, 4' -dicarboxylic acid prepared in example 1;
FIG. 5 is a graph of the ratio of intercalated pseudocapacitances based on 2,2 '-bipyridine-4, 4' -dicarboxylic acid prepared in example 1: (a) a pseudocapacitance effect map, (b) an insertion layer pseudocapacitance ratio map;
fig. 6 is an SEM image of a P (VDF-HFP) porous film prepared in example 1: (a) the scale bar is 20 μm; (b) the scale is 2 μm;
FIG. 7 is a physical photograph of a P (VDF-HFP) gel electrolyte membrane prepared in example 1;
FIG. 8 is a graph showing energy density at different mass ratios of positive and negative electrode active materials in a lithium ion capacitor containing 2,2 '-bipyridine-4, 4' -dicarboxylic acid prepared in example 1;
FIG. 9 is a constant current charge/discharge curve diagram of a lithium ion capacitor containing 2,2 '-bipyridine-4, 4' -dicarboxylic acid prepared in example 1 under the condition of an optimal mass ratio of positive and negative electrode active materials;
FIG. 10 is a graph of energy density versus power density for an optimum positive and negative electrode active material mass ratio for a lithium ion capacitor containing 2,2 '-bipyridine-4, 4' -dicarboxylic acid prepared in example 1;
FIG. 11 is a photograph of a flexible lithium ion hybrid capacitor of 2,2 '-bipyridine-4, 4' -dicarboxylic acid prepared in example 1 in real life and a practical example.
Detailed Description
The following provides a detailed description of preferred embodiments of the invention.
Example 1
The embodiment provides an organic nanometer negative electrode based on an insertion layer type pseudocapacitance and a preparation method and application thereof, and the preparation method specifically comprises the following steps:
preparation of 2,2 '-bipyridine-4, 4' -dicarboxylic acid electrode and performance test of lithium ion battery
(1) 2,2 '-bipyridine-4, 4' -dicarboxylic acid material is placed in a forced air drying oven and dried for 8 hours at 120 ℃;
(2) weighing 0.5g of 2,2 '-bipyridine-4, 4' -dicarboxylic acid, 0.4g of conductive carbon black and 0.1g of binder (polyvinylidene fluoride, commercially available) at room temperature, grinding for 10 minutes, then adding 20ml of solvent (N-methylpyrrolidone), fully stirring, grinding for 2 hours by high-energy ball milling, and then uniformly coating on a copper foil;
(3) drying at 60 ℃ for 3 hours, and then drying in vacuum at 120 ℃ to obtain a 2,2 '-bipyridine-4, 4' -dicarboxylic acid pole piece;
(4) taking the 2,2 '-bipyridine-4, 4' -dicarboxylic acid pole piece obtained in the step (3) as a negative pole, taking a lithium piece as the negative pole, and using 1mol/L LiPF6And assembling the button cell for the electrolyte in a glove box, and performing related electrochemical performance tests after standing for 6 hours.
Fig. 1 is an SEM image of the 2,2 '-bipyridine-4, 4' -dicarboxylic acid electrode sheet prepared in this example, and it can be seen that 2,2 '-bipyridine-4, 4' -dicarboxylic acid exhibits a lamellar structure, and the periphery is tightly adhered by conductive carbon black, which sufficiently ensures the conductivity of the electrode. FIG. 2 is a TEM image of the 2,2 '-bipyridine-4, 4' -dicarboxylic acid electrode sheet prepared in this example, which shows that 2,2 '-bipyridine-4, 4' -dicarboxylic acid is composed of 2-8 nm nanoparticlesMicron sheet structure composed of rice crystal. FIG. 3 is a graph of rate capability of the lithium ion battery with the 2,2 '-bipyridine-4, 4' -dicarboxylic acid electrode sheet prepared in this example, and it can be seen from the graph that the material has excellent rate capability, 20A g-1The capacity can reach 495mAh g under the current density of-1. FIG. 4 is a diagram of the cycle performance of the lithium ion battery with the 2,2 '-bipyridine-4, 4' -dicarboxylic acid electrode sheet prepared in this example, as shown in 2A g-1At a current density of (d), the capacity after 520 cycles is up to 731mAhg-1. Fig. 5 is a schematic diagram of the intercalation capacitance ratio of the lithium ion battery with the 2,2 '-bipyridine-4, 4' -dicarboxylic acid electrode sheet prepared in this example. As can be seen from FIG. 5(a), s is between 0.1 and 20mV-1In the sweep rate interval, the b values of the oxidation peak and the reduction peak are 0.85 and 0.86 respectively, which shows that the 2,2 '-bipyridyl-4, 4' -dicarboxylic acid has higher pseudocapacitance effect and thus has excellent rate performance. As can be seen from FIG. 5(b), 2,2 '-bipyridine-4, 4' -dicarboxylic acid was present at 2mV s-1Under the sweeping speed condition, the proportion of the intercalation pseudocapacitance is up to 91.4 percent.
(II) preparation of commercial porous activated carbon electrode
Commercial activated carbon, conductive carbon black and PVDF binder were mixed according to a 90: 5: 5, mixing and stirring the slurry according to a mass ratio, controlling the solid content to be about 10%, uniformly mixing the slurry under a high-speed shearing condition to obtain slurry of the active carbon anode, coating the slurry on an aluminum foil, and drying the slurry to obtain the porous active carbon electrode plate.
Pre-lithiation of (tri) 2,2 '-bipyridine-4, 4' -dicarboxylic acid electrodes
(1) The prepared 2,2 '-bipyridine-4, 4' -dicarboxylic acid pole piece is used as a positive pole, a lithium piece is used as a negative pole, and 1mol/L LiPF is used6Assembling a lithium ion half-cell for the electrolyte in a glove box, standing for 6 hours, and then carrying out a constant current charge-discharge test until the coulomb efficiency reaches over 90 percent and ending in a discharge state;
(2) after the pre-lithiation is finished, the battery is disassembled, the pole piece is cleaned by using solvents such as dimethyl carbonate and the like, lithium salt is fully removed, and the pole piece is dried for later use.
(IV) preparation of gel electrolyte
(1) P (VDF-HFP) (i.e., a commercial polyvinylidene fluoride-hexafluoropropylene copolymer powder), acetone, and water were mixed at a mass ratio of 0.8: 8: 4, then casting the solution on a glass plate to evaporate the acetone; after 1 hour, it was immersed in methanol to form pores, and then vacuum-dried at 80 degrees for 12 hours to obtain a P (VDF-HFP) film;
(2) after drying, the P (VDF-HFP) film was cut into disks, which were then impregnated with 1mol/L LiPF6The electrolyte is reserved; before assembling the lithium ion hybrid capacitor, the lithium ion hybrid capacitor was taken out and kept ready to obtain a P (VDF-HFP) film gel electrolyte film.
Fig. 6(a) and 6(b) are SEM images of the P (VDF-HFP) film, from which it can be seen that the P (VDF-HFP) film has a rich pore structure, and the diameter of each pore is about 2.5 um. FIG. 7 is a photograph showing a P (VDF-HFP) membrane and a P (VDF-HFP) gel electrolyte membrane impregnated with 1mol/L LiPF6After the electrolyte, the P (VDF-HFP) film exhibited a transparent property.
(V) Assembly of lithium ion hybrid capacitor
(1) Assembling a lithium ion hybrid capacitor in a glove box with the water/oxygen content of less than 0.1ppm by taking the pre-lithiated 2,2 '-bipyridyl-4, 4' -dicarboxylic acid organic electrode as a negative electrode and active carbon as a positive electrode, and assembling the lithium ion hybrid capacitor according to the sequence of a positive electrode shell, a positive electrode material, a gel electrolyte, an organic electrode pole piece and a negative electrode shell;
(2) after the assembly is finished, packaging the battery, standing for a period of time, and carrying out electrochemical performance test;
(3) and after standing, carrying out multiplying power and cycle test by constant current charging and discharging, wherein the voltage window is 0-5V, and charging and discharging are carried out firstly.
Fig. 8 is a graph showing a comparison of energy densities of capacitors at different mass ratios of the negative electrode active material. As can be seen from the figure, when the mass ratio of the negative electrode is 7: 1, the assembled capacitor has the highest energy density and the optimal rate performance. Fig. 9 shows that the mass ratio of the negative electrode is 7: 1 constant current charge/discharge profile of the capacitor. As can be seen from the figure, the assembled lithium ion hybrid capacitor has the highest voltage of 4.8V and better reversible performance. Fig. 10 shows that the mass ratio of the negative electrode is 7: 1 capacitanceEnergy density-power density plot of the device. As can be seen, when the power density is 120W kg-1At the time, the assembled lithium ion hybrid capacitor has the highest energy density of 178.7Wh kg-1When the energy density is 68.1kW kg-1The capacitor has a maximum power density of 24kW kg-1The performance of the lithium ion hybrid capacitor is remarkably superior to that of most lithium ion hybrid capacitors reported at present. Fig. 11 is an appearance view and a practical application schematic diagram of the assembled flexible lithium ion hybrid capacitor. It can be seen that the voltage of the capacitor can be charged to 4.8V, and 108 red LED lamps can be lighted.
Example 2
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material was fumaric acid, and the maximum energy density, maximum power density and cell voltage data of the whole cell are shown in table 1.
Example 3
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is sodium citrate, and the maximum energy density, the maximum power density and the cell voltage data of the whole cell are shown in table 1.
Example 4
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is cyclohexadecanone, and the maximum energy density, the maximum power density and the cell voltage data of the full cell are shown in table 1.
Example 5
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is 2,2 '-bipyridine-5, 5' -dicarboxylic acid, and the maximum energy density, the maximum power density and the cell voltage data of the whole cell are shown in table 1.
Example 6
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is maleic acid, and the maximum energy density, the maximum power density and the battery voltage data of the full battery are shown in table 1.
Example 7
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is itaconic acid, and the maximum energy density, the maximum power density and the cell voltage data of the full cell are shown in table 1.
Example 8
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material was terephthalic acid, and the maximum energy density, maximum power density and cell voltage data of the full cell are shown in table 1.
Example 9
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is naphthalene tetracarboxylic dianhydride, and the maximum energy density, the maximum power density and the battery voltage data of the whole battery are shown in table 1.
Example 10
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is perylenetetracarboxylic dianhydride, and the maximum energy density, the maximum power density and the battery voltage data of the whole battery are shown in table 1.
Example 11
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is lithium rhodizonate, and the maximum energy density, the maximum power density and the battery voltage data of the full battery are shown in table 1.
Example 12
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is rhodizonic acid tetralithium salt, and the maximum energy density, the maximum power density and the battery voltage data of the full battery are shown in table 1.
Example 13
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is hexalithium rhodizonate, and the maximum energy density, the maximum power density and the battery voltage data of the full battery are shown in table 1.
Example 14
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is sodium rhodizonate, and the maximum energy density, the maximum power density and the battery voltage data of the full battery are shown in table 1.
Example 15
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is lithium terephthalate, and the maximum energy density, the maximum power density and the battery voltage data of the whole battery are shown in table 1.
Example 16
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is 2, 4-dialkenyl lithium adipate, and the maximum energy density, the maximum power density and the cell voltage data of the whole cell are shown in table 1.
Example 17
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is azobenzene, and the maximum energy density, the maximum power density and the battery voltage data of the full battery are shown in table 1.
Example 18
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is 4- (benzene azo) sodium benzoate, and the maximum energy density, the maximum power density and the cell voltage data of the whole cell are shown in table 1.
Example 19
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is azobenzene-4, 4' -dicarboxylic acid sodium salt, and the maximum energy density, the maximum power density and the battery voltage data of the whole battery are shown in table 1.
Example 20
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material is polydopamine, and the maximum energy density, the maximum power density and the cell voltage data of the whole cell are shown in table 1.
Example 21
This example provides an organic nano-anode based on an insertion layer type pseudocapacitance, and a preparation method and an application thereof, which are substantially the same as those in example 1, except that: the organic electrode material was polymer PQL, and the maximum energy density, maximum power density, and cell voltage data of the full cell are shown in table 1.
Comparative example 1
This example provides an organic negative electrode, a method of making the same, and applications of the same, which are substantially the same as in example 1, except that: the organic electrode material is benzoquinone, which does not have a layered crystal structure and can only store lithium based on the oxidation-reduction reaction of carbon groups on a benzene ring, so that high-energy-density and rapid lithium ion storage cannot be realized, and an insertion-layer pseudocapacitance phenomenon cannot be caused.
TABLE 1 full cell Performance Table based on different nano organic molecular crystals in examples 1-21
Figure BDA0002562867900000101
Figure BDA0002562867900000111
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (9)

1. An organic nanometer negative electrode based on an insertion layer type pseudocapacitance comprises an active material, a conductive agent and a binder, and is characterized in that: the active material is an organic molecular crystal material, the crystal structure of the organic molecular crystal material is a hexagonal or monoclinic layered structure, and the interlayer distance is 0.2-0.6 nm.
2. The organic nanometer negative electrode based on the insertion layer type pseudocapacitance of claim 1 is characterized in that: the organic molecular crystal material is a mixture consisting of one or more of 2,2 '-bipyridyl-4, 4' -dicarboxylic acid, fumaric acid, cyclohexadecanone, organic conjugated micromolecule carboxylic acid, organic conjugated anhydride, organic conjugated quinones, organic conjugated sulfur, organic conjugated azobenzene and organic conductive polymers.
3. The organic nanometer negative electrode based on the insertion layer type pseudocapacitance of claim 2 is characterized in that: the organic molecular crystal material is a mixture consisting of one or more of 2,2 '-bipyridyl-3, 3' -dicarboxylic acid, 2 '-bipyridyl-5, 5' -dicarboxylic acid, maleic acid, itaconic acid, terephthalic acid, naphthalene tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, azobenzene, and polydopamine.
4. The organic nanometer negative electrode based on the insertion layer type pseudocapacitance of claim 1 is characterized in that: the mass ratio of the active material to the conductive agent to the binder is 5-8: 1-4: 1.
5. The organic nanometer negative electrode based on the insertion layer type pseudocapacitance of claim 1 is characterized in that: the binder is a mixture consisting of one or more of polyvinylidene fluoride, carboxymethyl cellulose, sodium alginate, LA132, lignocellulose and polytetrafluoroethylene.
6. The method for preparing the organic nanometer negative electrode based on the insertion layer type pseudocapacitance is characterized by comprising the following steps:
(a) mixing the active material, the conductive agent and the binder, adding a solvent, and performing ball milling to obtain viscous slurry;
(b) coating the viscous slurry on a metal foil, and drying to obtain a pole piece;
(c) and rolling and punching the pole piece.
7. The method for preparing the organic nanometer negative electrode based on the insertion layer type pseudocapacitance is characterized in that: in the step (a), the solvent is a mixture of one or more selected from N-methyl pyrrolidone, water and ethanol.
8. The use of the organic nano-anode based on the intercalation pseudocapacitance as claimed in any one of claims 1 to 5, wherein: the lithium ion battery is used for assembling a lithium ion hybrid capacitor with a positive electrode and an electrolyte.
9. The application of the organic nanometer negative electrode based on the insertion layer type pseudocapacitance as claimed in claim 8, wherein: the active material of the positive electrode is commercial porous activated carbon, S-doped porous carbon, N-doped porous carbon, P-doped porous carbon, biomass-derived porous activated carbon or metal organic framework-derived porous carbon.
CN202010613224.5A 2020-06-30 2020-06-30 Organic nanometer negative electrode based on insertion layer type pseudo-capacitor and preparation method and application thereof Active CN111696792B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010613224.5A CN111696792B (en) 2020-06-30 2020-06-30 Organic nanometer negative electrode based on insertion layer type pseudo-capacitor and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010613224.5A CN111696792B (en) 2020-06-30 2020-06-30 Organic nanometer negative electrode based on insertion layer type pseudo-capacitor and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111696792A CN111696792A (en) 2020-09-22
CN111696792B true CN111696792B (en) 2021-07-20

Family

ID=72484642

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010613224.5A Active CN111696792B (en) 2020-06-30 2020-06-30 Organic nanometer negative electrode based on insertion layer type pseudo-capacitor and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111696792B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335476B (en) * 2021-12-31 2023-08-11 蜂巢能源科技股份有限公司 Preparation method and application of anode material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104409223A (en) * 2014-11-21 2015-03-11 中国科学院青岛生物能源与过程研究所 Lithium ion capacitor cathode piece and lithium ion capacitor using cathode pieces
CN109243831A (en) * 2017-07-10 2019-01-18 清华大学深圳研究生院 Lithium-ion capacitor and preparation method thereof

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010012481A (en) * 1997-05-08 2001-02-15 에이. 조아렌스 데이비드 Adsorbent refrigerator with separator
JPH11345629A (en) * 1998-03-31 1999-12-14 Canon Inc Secondary battery and production of the same
JP5240808B2 (en) * 2006-02-24 2013-07-17 国立大学法人大阪大学 Molecular crystalline secondary battery
JP2008287976A (en) * 2007-05-16 2008-11-27 Toyota Motor Corp Coordination polymer complex compound
US20090047567A1 (en) * 2007-08-16 2009-02-19 Sony Corporation Biofuel cell, method for producing the same, electronic apparatus, enzyme-immobilized electrode, and method for producing the same
JP5298479B2 (en) * 2007-08-17 2013-09-25 ソニー株式会社 Fuel cells and electronics
CN101937989A (en) * 2010-08-13 2011-01-05 上海中科深江电动车辆有限公司 Three-dimensional nanoporous metal-oxide electrode material of lithium ion battery and preparation method thereof
US8795893B2 (en) * 2010-10-21 2014-08-05 Kabushiki Kaisha Toyota Chuo Kenkyusho Nonaqueous secondary battery electrode, nonaqueous secondary battery including the same, and assembled battery
CN102659845B (en) * 2012-03-30 2015-02-04 常州大学 Layered metal coordination polymer and synthesis method thereof
CN105131321A (en) * 2014-06-04 2015-12-09 苏州高通新材料科技有限公司 Method for treatment of organic polymer material with acid, and functionalized-graphene-containing powder product with carbon material attached to the surface
CN105047897B (en) * 2015-09-09 2018-09-14 芜湖雄狮汽车科技有限公司 A kind of preparation method of anode material for lithium-ion batteries, lithium ion battery
CN107359314A (en) * 2016-05-10 2017-11-17 北京化工大学 A kind of synthetic method of negative electrode of lithium ion battery lithium titanate/carbon composite
CN108467502B (en) * 2018-04-03 2021-01-08 电子科技大学 Preparation method of porous composite nano film material
CN109713297B (en) * 2018-12-26 2022-03-29 宁波容百新能源科技股份有限公司 High-nickel anode material with directionally arranged primary particles and preparation method thereof
CN110010894A (en) * 2019-04-11 2019-07-12 南开大学 A kind of triqunioyl material and preparation method thereof for lithium ion cell positive

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104409223A (en) * 2014-11-21 2015-03-11 中国科学院青岛生物能源与过程研究所 Lithium ion capacitor cathode piece and lithium ion capacitor using cathode pieces
CN109243831A (en) * 2017-07-10 2019-01-18 清华大学深圳研究生院 Lithium-ion capacitor and preparation method thereof

Also Published As

Publication number Publication date
CN111696792A (en) 2020-09-22

Similar Documents

Publication Publication Date Title
Wang et al. Application of carbon materials in aqueous zinc ion energy storage devices
CN102290245B (en) Polyimide capacitor battery and manufacturing method thereof
US20120321913A1 (en) Manufacturing method for long-lived negative electrode and capacitor battery adopting the same
US20170174872A1 (en) Aqueous composite binder of natural polymer derivative-conducting polymer and application thereof
CN108183039B (en) Preparation method of carbon-modified titanium niobate material, lithium ion capacitor and negative electrode slurry thereof
CN108520947A (en) Modified phosphate iron lithium material, lithium ion battery, power battery pack and its application
US20130155577A1 (en) Capacitor cell with high-specific-energy organic system
CN108682820B (en) Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery
CN101154750A (en) High power gel polymer lithium ion power cell and method of producing the same
CN110364761B (en) High-energy-density long-circulation lithium iron phosphate battery
CN103035901B (en) Nanometer oxide coated lithium titanate negative electrode material of lithium battery, and preparation method for negative electrode material
CN112614703B (en) Negative electrode material of ionic capacitor and preparation method and application thereof
CN105226274A (en) Preparation method of lithium iron phosphate/graphene composite material with uniformly dispersed graphene
CN117174873A (en) Preparation method of positive electrode material, positive electrode plate, sodium ion battery and power utilization device
CN102456866A (en) Organic free radical polymer electrode as well as preparation and application for same
CN105390295A (en) Lithium-ion capacitor, and negative material and negative electrode plate thereof
CN101414679A (en) Composite material and preparation method thereof, and cathode and lithium battery
CN111696792B (en) Organic nanometer negative electrode based on insertion layer type pseudo-capacitor and preparation method and application thereof
CN107221699A (en) A kind of novel high voltage lithium ion battery and energy storage elements based on silicium cathode
WO2007009363A1 (en) An electrochemical supercapacitor using organic polymer free radical /carbon composite material as positive electrode
CN111509189A (en) Positive pole piece and lithium ion battery
CN115275166A (en) Long-life graphite composite material and preparation method thereof
CN114864916A (en) Niobium pentoxide coated graphite composite negative electrode material and preparation method thereof
CN101527370A (en) Power lithium ion battery
CN115172680A (en) High-capacity high-rate lithium ion battery and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant