CN112614703B - Negative electrode material of ionic capacitor and preparation method and application thereof - Google Patents
Negative electrode material of ionic capacitor and preparation method and application thereof Download PDFInfo
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- CN112614703B CN112614703B CN202011372223.2A CN202011372223A CN112614703B CN 112614703 B CN112614703 B CN 112614703B CN 202011372223 A CN202011372223 A CN 202011372223A CN 112614703 B CN112614703 B CN 112614703B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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 relates to an ion capacitor cathode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: uniformly mixing metaphosphate with a carbon-based negative electrode material; then, carrying out metaphosphate coating on the carbon-based negative electrode material by a solid phase method to prepare an active material, and then mixing the active material with a conductive agent, a binder and a current collector to prepare a negative electrode material; (2) And assembling the negative electrode material, the diaphragm, the electrolyte and the lithium sheet into a button type half cell, and pre-embedding the button type half cell by a small-rate current electrochemical method of metal elements to obtain the negative electrode material of the ionic capacitor. Compared with the prior art, the lithium ion secondary battery has the advantages of capability of inhibiting lithium dendrite generation, high cycle stability, high first coulombic efficiency, high energy density of a capacitor and the like.
Description
Technical Field
The invention relates to the field of electrochemistry, and particularly relates to an ion capacitor cathode material, and a preparation method and application thereof.
Background
With the rapid development of economic society, new energy is receiving attention as a strategic emerging industry of the country. As an important support and auxiliary technology of new energy industry, energy storage technology is concerned by all parties. The development of energy storage devices with high energy density and high power density is particularly important in the face of the important requirements of electric automobiles, wind power generation, urban rail transit, power grid equipment, emergency power supplies, heavy trucks, port machinery and the like. A Lithium Ion Capacitor (LIC) is a hybrid Capacitor, and usually stores electric energy in a Lithium-based organic electrolyte system by using the principle of negative electrode electrochemical Lithium intercalation combined with positive electrode charge adsorption.
Compared with the double electric layer capacitor, the total specific capacity and the working voltage of the capacitor are remarkably improved, the energy density is greatly improved while the power characteristic is kept, and the capacitor has the characteristics of high power, long service life, high energy density of a lithium ion battery and the like. Therefore, the method faces to the national important requirements, develops the high-performance lithium ion capacitor and the key preparation technology thereof, solves the key problem in the process of developing the lithium ion capacitor, can provide powerful support for low-carbon economy and social sustainable development, and further improves the innovation capability of the new technology development source in China.
The energy density of a lithium ion capacitor depends mainly on the specific capacitance of the electrode material and the operating voltage of the electrode material in the electrolyte. The electrode material and the electrolyte are the determining factors for determining the performance of the lithium ion capacitor. From the analysis of electrode materials, the energy density of carbon-based lithium ion capacitors, which are mainly activated carbon materials in the prior art, is generally low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an ion capacitor negative electrode material which can inhibit lithium dendrite generation, has high cycle stability, high first coulombic efficiency and high capacitor energy density, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
from the analysis of electrode materials, for carbon-based lithium ion capacitors, energy storage through an electric double layer is a physical process of surface adsorption, and no bulk phase atoms participate, so that the energy density of the lithium ion capacitors adopting the activated carbon materials is generally low.
The inventor knows that to improve the energy density of the lithium ion capacitor, the influence of the microstructure, the composition and the distribution of the electrode material on the specific capacitance of the electrode material must be known, the carbon material with the controllable pore structure is prepared by adopting a new process, and the physicochemical property of the carbon material is adjusted by other physical and chemical means.
The pre-embedded lithium is the most important part in the research and development process of the lithium ion capacitor, the pre-embedded lithium amount is difficult to be accurately controlled by adopting a cut-off voltage limiting method, and a certain safety problem also exists by adopting a mode of directly short-circuiting a negative electrode and a lithium source. Based on the analysis, the invention develops a lithium intercalation technology which can accurately control the lithium intercalation amount and has no safety problem, is the most core and the most key means of the lithium ion capacitor, and has the following specific scheme:
a preparation method of an ion capacitor negative electrode material comprises the following steps:
(1) Uniformly mixing metaphosphate with the carbon-based negative electrode material; performing metaphosphate coating on the carbon-based negative electrode material by a solid phase method to prepare an active material so as to finish physical inlaying of metal elements, and then mixing the active material with a conductive agent, a binder and a current collector to prepare a negative electrode material;
(2) And assembling the negative electrode material, the diaphragm, the electrolyte and the lithium sheet into a button type half cell, and pre-embedding the button type half cell by a small-rate current electrochemical method of metal elements to obtain the negative electrode material of the ionic capacitor.
Further, the uniform mixing is to mix metaphosphate and carbon-based negative electrode material by adopting ethanol solution and then carry out wet mixing in a ball milling or sanding way, wherein the time of ball milling or sanding is 2-18h. Preferably, the mixing is wet ball milling, the ball milling time is 18h, and the rotating speed is 200-350rpm.
Further, the solid phase method is that under the argon atmosphere, the temperature is raised to 400-800 ℃ at the temperature rise rate of 2-10 ℃/min, the calcination is carried out for 2-10h, and then the natural cooling is carried out to the room temperature under the argon atmosphere. Preferably, the calcining temperature is 600-800 ℃, and the calcining time is 6h.
Further, the conductive agent is graphene, carbon nanotubes, conductive carbon black: such as acetylene black, superP, superS, 350G, ketjen black, graphite conductive agents: such as KS-6, KS-15, SFG-6, SFG-15, carbon fiber-based conductive agents;
the binder is polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), olefins (PE and other copolymers), polyvinylidene fluoride/N-methyl pyrrolidone (PVDF/NMP);
the current collector is an aluminum current collector (containing carbon-coated aluminum foil), a copper current collector, a nickel current collector, a stainless steel current collector, a carbon current collector or a composite current collector;
the electrolyte is an organic solution of lithium salt; the lithium salt is lithium perchlorate, lithium hexafluorophosphate or lithium tetrafluoroborate, and the organic solvent in the electrolyte is propylene carbonate, ethylene carbonate, ethyl carbonate, dimethyl carbonate or methyl ethyl carbonate;
the diaphragm is a Celgard diaphragm or a cellulose paper diaphragm.
Further, the electrochemical method comprises one-time discharge or three-time cycle charge and discharge;
in the primary discharge: assembling into a half cell, wherein the discharge rate is 0.05C, the mosaic quantity is 0-250mAh/g, preferably 250mAh/g, and the discharge cut-off voltage is 0.05V;
in the three times of charge and discharge: the semi-cell is assembled, the charge-discharge multiplying power is 0.05C, and the charge-discharge cut-off voltage is 0.05-3V.
Further, the metaphosphate comprises one or more of lithium metaphosphate, aluminum metaphosphate, niobium metaphosphate, lanthanum metaphosphate, magnesium metaphosphate, yttrium metaphosphate or neodymium metaphosphate;
the carbon-based negative electrode material comprises one or more of soft carbon, hard carbon, graphite or mesocarbon microbeads.
Further, the metaphosphate is 1-7% by mass, preferably 3% by mass, in the negative electrode material.
Further, the ionic capacitor comprises a lithium ion capacitor, a sodium ion capacitor, a magnesium ion capacitor, an aluminum ion capacitor, a zinc ion capacitor or a calcium ion capacitor.
The negative electrode material of the ion capacitor manufactured by the method.
The application of the negative electrode material of the ion capacitor, which is assembled with the positive electrode active material, the electrolyte and the diaphragm into the ion capacitor;
the positive active material comprises a porous carbon-based material or a conductive polymer, a conductive agent, a binder and a current collector; the porous carbon-based material is activated carbon fiber, activated carbon powder, carbon nano tube or graphene, or a mixture of one of lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, lithium nickel cobalt manganese aluminate or lithium cobalt oxide and one of activated carbon fiber, activated carbon powder, carbon nano tube or graphene; the conductive polymer is polyaniline, polyparaphenylene, polypyrrole or polythiophene and derivatives thereof; the conductive agent is graphene, carbon nanotubes, conductive carbon black: such as acetylene black, superP, superS, 350G, ketjen black, graphite conductive agents: such as KS-6, KS-15, SFG-6, SFG-15, carbon fiber-based conductive agents; the binder is polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), olefins (PE and other copolymers), polyvinylidene fluoride/N-methylpyrrolidone (PVDF/NMP); the current collector is an aluminum current collector (containing carbon-coated aluminum foil), a copper current collector, a nickel current collector, a stainless steel current collector, a carbon current collector or a composite current collector;
the electrolyte is an organic solution of lithium salt; the lithium salt is lithium perchlorate, lithium hexafluorophosphate or lithium tetrafluoroborate, and the organic solvent in the electrolyte is propylene carbonate, ethylene carbonate, ethyl carbonate, dimethyl carbonate or methyl ethyl carbonate;
the diaphragm is a Celgard diaphragm or a cellulose paper diaphragm.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the metaphosphate is attached to the surface of the carbon-based negative electrode material through physical coating, and a coating layer with a similar glass shape is formed at high temperature, so that the contact between the electrolyte and the carbon-based negative electrode material can be effectively isolated, the occurrence of side reaction is avoided, the generation of lithium dendrite can be inhibited, the lithium intercalation amount is increased, and the cycle stability of the lithium intercalation amount is improved;
(2) According to the invention, physical coating and electrochemical lithium intercalation are combined, so that the lithium intercalation amount is further increased on the premise of maintaining the original effect, and the improvement of the first coulomb efficiency is realized;
(3) The invention only needs to add a little metaphosphate, has simple preparation method, does not cause high economic cost, further improves the energy density of the lithium ion capacitor, and is a lithium intercalation technology with industrial production potential;
(4) According to the invention, the HC is pre-intercalated with lithium in an electrochemical lithium intercalation mode, and the effect after lithium intercalation in three times of charge and discharge is obviously superior to that after lithium intercalation in one time of discharge by comparing the lithium intercalation in one time with the lithium intercalation in three times; and the lithium intercalation amount and the coulombic efficiency of the hard carbon are improved by combining a physical coating method and a pre-lithium intercalation technology, and the electrochemical lithium intercalation can accurately control the pre-lithiation degree.
Drawings
FIG. 1 is a graph showing discharge curves of different degrees of lithium intercalation in one-time discharge in example 1;
FIG. 2 is a lithium intercalation curve of three-time charge-discharge lithium intercalation in example 2;
FIG. 3 is a first charge and discharge curve of a hard carbon negative electrode of examples 1, 3-6 with 0%, 1%, 3%, 5%, 7% lithium metaphosphate added thereto;
fig. 4 is a rate test curve for hard carbon anodes with 0% and 1% lithium metaphosphate added for example 3;
fig. 5 is a cycle test curve for hard carbon anodes with 0% and 1% lithium metaphosphate added as in example 3;
fig. 6 is a rate test curve for hard carbon anodes with 0% and 3% lithium metaphosphate added for example 4;
fig. 7 is a cycle test curve for hard carbon anodes with 0% and 3% lithium metaphosphate addition for example 4;
fig. 8 is a rate test curve for hard carbon anodes with 0% and 5% lithium metaphosphate added for example 5;
fig. 9 is a cycle test curve for hard carbon anodes with 0% and 5% lithium metaphosphate added as in example 5;
fig. 10 is a rate test curve for hard carbon anodes with 0% and 7% lithium metaphosphate added as in example 6;
fig. 11 is a cycle test curve for hard carbon anodes with 0% and 7% lithium metaphosphate addition for example 6;
FIG. 12 is a flow chart of the manufacturing process of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A lithium intercalation method for primary discharge of a lithium ion capacitor is characterized in that primary discharge is carried out through low-rate current (0.05C) to pre-intercalate lithium into hard carbon, as shown in figure 1, the lithium intercalation amount is respectively 0, 100, 150, 200 and 250mAh/g, wherein the lithium intercalation termination voltage is 0.05V, and the lithium intercalation process is completed in a button type half cell consisting of a hard carbon cathode, a diaphragm, electrolyte and a lithium piece.
The hard carbon negative electrode comprises a hard carbon active material, a conductive agent Super P, a binder PVDF, a copper current collector and the like, wherein the mass ratio of the active material to the conductive agent to the binder is 90; the diaphragm is Celgard diaphragm 2325; the electrolyte contains 1.2M LiPF 6 EC of electrolyte EMC DMC = 1.
As can be seen from FIG. 1, the lithium intercalation termination voltage is 0.1029V and still higher than 0.05V when lithium intercalation is carried out to 250 mAh/g.
Example 2
A lithium intercalation method for three-time charge and discharge of a lithium ion capacitor is characterized in that three-time cycle charge and discharge are carried out on hard carbon within a lithium intercalation voltage interval of 0.05-3V by small-rate current (0.05C), as shown in figure 2, and the lithium intercalation process is completed in half-buckling electricity consisting of a hard carbon cathode, a diaphragm, electrolyte and a lithium sheet. The third lithium intercalation amount is 231.5mAh/g.
The hard carbon negative electrode comprises a hard carbon active material, a conductive agent Super P, a binder PVDF, a copper current collector and the like, wherein the mass ratio of the active material to the conductive agent to the binder is (90); the septum is Celgard2325; the electrolyte contains 1.2M LiPF 6 EC of electrolyte EMC DMC = 1.
Compared with the embodiment 1, the lithium intercalation effect after three times of charge and discharge is obviously superior to that of the lithium intercalation effect after one time of discharge. Therefore, in the subsequent examples, lithium intercalation behavior after coating is studied, and a lithium intercalation form is adopted for three times of charge and discharge.
Example 3
A method of lithium insertion for a lithium ion capacitor, the method comprising the steps of:
(1) Uniformly mixing 1% lithium metaphosphate and hard carbon in a ball milling mode, wherein a ball milling solvent is absolute ethyl alcohol, the ball milling time is 18 hours, and the ball milling rotating speed is 350rpm. And then placing the uniformly mixed composite material in a tubular furnace, taking argon as a calcining atmosphere, raising the temperature to 600 ℃ at the temperature rise rate of 2 ℃/min, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the calcined material.
(2) The lithium intercalation process is finally completed in a button type half cell consisting of a hard carbon cathode, a diaphragm, electrolyte and a lithium sheet by carrying out three times of cyclic charge and discharge on the hard carbon coated with 1% of lithium metaphosphate within a lithium intercalation voltage interval of 0.05-3V by virtue of a small rate current (0.05C). The hard carbon negative electrode comprises 1% of lithium metaphosphate coated hard carbon, a conductive agent Super P, a binder PVDF, a copper current collector and the like, wherein the mass ratio of an active material, the conductive agent and the binder is 90; the septum is Celgard2325; the electrolyte contains 1.2M LiPF 6 EC of electrolyte: DMC = 1.
Then assembling the pole pieces after lithium intercalation into a full-buckling type lithium ion capacitor, wherein the lithium intercalation pole piece is used as a negative electrode, the active carbon is used as a positive electrode and the lithium intercalation pole piece contains LiPF 6 The EC of (1) is EMC, DMC =1, 1 is electrolyte, celgard2325 is diaphragm; the active carbon positive electrode comprises an active carbon material, a conductive agent Super P, a binder PTFE, an aluminum current collector and the like, wherein the mass ratio of the active material to the conductive agent to the binder is 90.
Compared with the embodiment 2, as shown in figure 3, the lithium intercalation amount of the hard carbon can be improved by adding 1% of lithium metaphosphate, and the lithium intercalation amount is 496.1mAh/g; as shown in fig. 4, the rate discharge capacity is equivalent to that of the original hard carbon; as shown in fig. 5, the capacity retention rate after 100 cycles at a charge-discharge rate of 1C was 91.6%, which is greater than 88.72% of the original hard carbon. In conclusion, the electrochemical performance of the lithium ion capacitor can be improved by combining physical coating and electrochemical lithium intercalation.
Example 4
A method of lithium insertion for a lithium ion capacitor, the method comprising the steps of:
(1) Uniformly mixing 3% lithium metaphosphate and hard carbon in a ball milling mode, wherein a ball milling solvent is absolute ethyl alcohol, the ball milling time is 18 hours, and the ball milling rotating speed is 350rpm. And then placing the uniformly mixed composite material in a tube furnace, taking argon as a calcining atmosphere, raising the temperature to 600 ℃ at the temperature rise rate of 2 ℃/min, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the calcined material.
(2) The lithium intercalation process is completed in half-charging consisting of a hard carbon cathode, a diaphragm, electrolyte and a lithium sheet by performing three-time cyclic charge and discharge on 3% lithium metaphosphate coated hard carbon within a lithium intercalation voltage interval of 0.05-3V through a small-rate current (0.05C). The hard carbon negative electrode comprises 3% lithium metaphosphate coated hard carbon, a conductive agent Super P, a binder PVDF, a copper current collector and the like, wherein the mass ratio of an active material to the conductive agent to the binder is (90); the diaphragm is Celgard2325; the electrolyte contains 1.2M LiPF 6 EC of electrolyte: DMC = 1.
Then assembling the pole pieces after lithium intercalation into a full-buckling type lithium ion capacitor, wherein the lithium intercalation pole piece is used as a negative electrode, the active carbon is used as a positive electrode and the lithium intercalation pole piece contains LiPF 6 The EC of (1) is EMC, DMC =1, 1 is electrolyte, celgard2325 is diaphragm; the active carbon positive electrode comprises an active carbon material, a conductive agent Super P, a binder PTFE, an aluminum current collector and the like, wherein the mass ratio of the active material to the conductive agent to the binder is 90.
Compared with the examples 2-3, as shown in FIG. 3, the addition of 3% of lithium metaphosphate can increase the lithium insertion amount of the hard carbon, and the lithium insertion amount is 515.3mAh/g; as shown in fig. 6, the rate discharge capacity is superior to that of the original hard carbon; as shown in fig. 7, after 100 cycles of cycling at a rate of 1C, the capacity retention rate is 96.9%, which is greater than 88.72% of the original hard carbon, and the electrochemical performance of the lithium ion capacitor can be improved by combining physical coating and electrochemical lithium intercalation. In summary, the effect by adding 3% lithium metaphosphate is better than 1%.
Example 5
A method of lithium insertion for a lithium ion capacitor, the method comprising the steps of:
(1) Uniformly mixing 5% lithium metaphosphate and hard carbon in a ball milling mode, wherein a ball milling solvent is absolute ethyl alcohol, the ball milling time is 18 hours, and the ball milling rotating speed is 350rpm. And then placing the uniformly mixed composite material in a tube furnace, taking argon as a calcining atmosphere, raising the temperature to 600 ℃ at the temperature rise rate of 2 ℃/min, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the calcined material.
(2) The lithium intercalation process is completed in half-charging consisting of a hard carbon cathode, a diaphragm, electrolyte and a lithium sheet by carrying out three times of cyclic charging and discharging on 5 percent lithium metaphosphate coated hard carbon within a lithium intercalation voltage interval of 0.05-3V through a small-rate current (0.05C). The hard carbon negative electrode comprises 5% lithium metaphosphate coated hard carbon, a conductive agent Super P, a binder PVDF, a copper current collector and the like, wherein the mass ratio of an active material to the conductive agent to the binder is (90); the diaphragm is Celgard2325; the electrolyte contains 1.2M LiPF 6 EC of electrolyte EMC DMC = 1;
then assembling the pole pieces after lithium intercalation into a full-buckling type lithium ion capacitor, wherein the lithium intercalation pole piece is taken as a negative electrode, the activated carbon is taken as a positive electrode and the LiPF is contained 6 The EC of (1) is that the EMC is DMC = 1; the active carbon positive electrode comprises an active carbon material, a conductive agent Super P, a binder PTFE, an aluminum current collector and the like, wherein the mass ratio of the active material to the conductive agent to the binder is 90.
Compared with the embodiment 2 and the embodiment 4, as shown in figure 3, after 5 percent of lithium metaphosphate, the lithium insertion amount is 450.6mAh/g; as shown in fig. 8, the rate discharge capacity is lower than that of the original hard carbon; as shown in fig. 9, after 100 cycles of cycling at a rate of 1C, the capacity retention rate is 91.5%, which is greater than 88.72% of the original hard carbon, and the electrochemical performance of the lithium ion capacitor can be improved by combining physical coating and electrochemical lithium intercalation. In summary, the effect by adding 3% lithium metaphosphate is better than 5%, which may be caused by excessive addition of lithium metaphosphate.
Example 6
A method of lithium insertion for a lithium ion capacitor, the method comprising the steps of:
(1) Uniformly mixing 7% lithium metaphosphate and hard carbon in a ball milling mode, wherein a ball milling solvent is absolute ethyl alcohol, the ball milling time is 18 hours, and the ball milling rotating speed is 350rpm. And then placing the uniformly mixed composite material in a tubular furnace, taking argon as a calcining atmosphere, raising the temperature to 600 ℃ at the temperature rise rate of 2 ℃/min, keeping the temperature for 6 hours, naturally cooling to room temperature, and taking out the calcined material.
(2) The hard carbon coated with 7% lithium metaphosphate is subjected to three times of cyclic charge and discharge within a lithium intercalation voltage interval of 0.05-3V by virtue of a small-rate current (0.05C), and the lithium intercalation process is completed in half-charging consisting of a hard carbon cathode, a diaphragm, electrolyte and a lithium sheet. The hard carbon negative electrode comprises 7% lithium metaphosphate coated hard carbon, a conductive agent Super P, a binder PVDF, a copper current collector and the like, wherein the mass ratio of an active material to the conductive agent to the binder is (90); the diaphragm is Celgard2325; the electrolyte contains 1.2M LiPF 6 EC of electrolyte EMC DMC = 1.
Then assembling the pole pieces after lithium intercalation into a full-buckling type lithium ion capacitor, wherein the lithium intercalation pole piece is used as a negative electrode, the active carbon is used as a positive electrode and the lithium intercalation pole piece contains LiPF 6 The EC of (1) is that the EMC is DMC = 1; the active carbon positive electrode comprises an active carbon material, a conductive agent Super P, a binder PTFE, an aluminum current collector and the like, wherein the mass ratio of the active material to the conductive agent to the binder is 90.
As compared with examples 2 and 4, as shown in FIG. 3, after 7% of lithium metaphosphate, the amount of lithium insertion was 327.9mAh/g; as shown in fig. 10, the rate discharge capacity is lower than that of the original hard carbon; as shown in fig. 11, after 100 cycles at a rate of 1C, the capacity retention rate is 88.9%, which is greater than 88.72% of the original hard carbon, and the electrochemical performance of the lithium ion capacitor can be improved by combining physical coating and electrochemical lithium intercalation. In summary, the effect by adding 3% lithium metaphosphate is better than that of 7%, which may be caused by excessive addition of lithium metaphosphate.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention will still fall within the protection scope of the technical solution of the present invention.
Claims (5)
1. The preparation method of the negative electrode material of the ionic capacitor is characterized by comprising the following steps of:
(1) Uniformly mixing metaphosphate with the carbon-based negative electrode material; then, carrying out metaphosphate coating on the carbon-based negative electrode material by a solid phase method to prepare an active material, and then mixing the active material with a conductive agent, a binder and a current collector to prepare a negative electrode material; the metaphosphate is lithium metaphosphate; the carbon-based negative electrode material is hard carbon; the mass content of metaphosphate in the negative electrode material is 1-3%; the conductive agent is graphene, a carbon nano tube, conductive carbon black, a graphite conductive agent and a carbon fiber conductive agent; the uniform mixing is to mix metaphosphate and carbon-based negative electrode material by ethanol solution and then carry out wet mixing in a ball milling or sanding way, wherein the time of ball milling or sanding is 2-18 h;
the solid phase method is that the temperature is raised to 400-800 ℃ at the temperature rise rate of 2-10 ℃/min under the argon atmosphere, the calcination is carried out for 2-10h, and then the mixture is naturally cooled to the room temperature under the argon atmosphere;
(2) Assembling a negative electrode material, a diaphragm, electrolyte and a lithium sheet into a button type half cell, and pre-embedding a metal element by an electrochemical method with low-rate current to obtain a negative electrode material of an ionic capacitor;
the electrochemical method comprises three times of cyclic charge and discharge; in the three-cycle charge and discharge: the semi-cell is assembled, the charge-discharge multiplying power is 0.05C, and the charge-discharge cut-off voltage is 0.05-3V.
2. The method for preparing the negative electrode material for ionic capacitors as claimed in claim 1,
the binder is polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), olefin, polyvinylidene fluoride/N-methyl pyrrolidone (PVDF/NMP);
the current collector is an aluminum current collector, a copper current collector, a nickel current collector, a stainless steel current collector, a carbon current collector or a composite current collector;
the electrolyte is an organic solution of lithium salt; the lithium salt is lithium perchlorate, lithium hexafluorophosphate or lithium tetrafluoroborate, and the organic solvent in the electrolyte is propylene carbonate, ethylene carbonate, ethyl carbonate, dimethyl carbonate or methyl ethyl carbonate;
the diaphragm is a Celgard diaphragm or a cellulose paper diaphragm.
3. The method for preparing the negative electrode material of the ionic capacitor as claimed in claim 1, wherein the ionic capacitor comprises a lithium ion capacitor, a sodium ion capacitor, a magnesium ion capacitor, an aluminum ion capacitor, a zinc ion capacitor or a calcium ion capacitor.
4. An ion capacitor negative electrode material produced by the method according to any one of claims 1 to 3.
5. Use of the negative electrode material for an ion capacitor according to claim 4, wherein the negative electrode material is assembled with a positive electrode active material, an electrolyte and a separator into an ion capacitor;
the positive active material comprises a porous carbon-based material or a conductive polymer, a conductive agent, a binder and a current collector; the porous carbon-based material is activated carbon fiber, activated carbon powder, carbon nano tube or graphene, or a mixture of one of lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, lithium nickel cobalt manganese aluminate or lithium cobalt oxide and one of activated carbon fiber, activated carbon powder, carbon nano tube or graphene; the conductive polymer is polyaniline, polypyrrole or polythiophene and derivatives thereof; the conductive agent is graphene, carbon nano tubes, conductive carbon black, a graphite conductive agent and a carbon fiber conductive agent; the binder is polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), olefins, polyvinylidene fluoride/N-methyl pyrrolidone (PVDF/NMP); the current collector is an aluminum current collector, a copper current collector, a nickel current collector, a stainless steel current collector, a carbon current collector or a composite current collector;
the electrolyte is an organic solution of lithium salt; the lithium salt is lithium perchlorate, lithium hexafluorophosphate or lithium tetrafluoroborate, and the organic solvent in the electrolyte is propylene carbonate, ethylene carbonate, ethyl carbonate, dimethyl carbonate or methyl ethyl carbonate;
the diaphragm is a Celgard diaphragm or a cellulose paper diaphragm.
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