CN109524243B - All-fiber type lithium ion capacitor and preparation method thereof - Google Patents

All-fiber type lithium ion capacitor and preparation method thereof Download PDF

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CN109524243B
CN109524243B CN201811490604.3A CN201811490604A CN109524243B CN 109524243 B CN109524243 B CN 109524243B CN 201811490604 A CN201811490604 A CN 201811490604A CN 109524243 B CN109524243 B CN 109524243B
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aramid
fiber
pulp
fiber paper
carbon
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CN109524243A (en
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孙晓刚
郑典模
蔡满园
聂艳艳
陈珑
潘鹤政
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HENAN KELAIWEI NANO CARBON MATERIAL Co.,Ltd.
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Jiangxi Kelaiwei Carbon Nano Materials Co ltd
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    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • 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
    • 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
    • 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
    • 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

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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Manufacturing & Machinery (AREA)
  • Paper (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention belongs to the technical field of electrochemistry, and particularly relates to an all-fiber lithium ion capacitor and a preparation method thereof. The invention takes the activated carbon-aramid fiber as the anode and the pre-lithiated carbon nanotube-aramid fiber paper as the cathode material to form the all-fiber type lithium ion capacitor, and the lithium ion capacitor has higher energy density and cycle performance. The example result shows that when the current density is 100mA/g, the discharge energy density of the all-fiber lithium ion capacitor provided by the invention is 94.5Wh/g, and when the current density is 1500mA/g, the discharge energy density reaches 72 Wh/g; the energy density retention rate of the alloy is about 80 percent after being cycled 6000 times under the current density of 100 mA/g.

Description

All-fiber type lithium ion capacitor and preparation method thereof
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to an all-fiber lithium ion capacitor and a preparation method thereof.
Background
The lithium ion capacitor is a novel energy storage device between the lithium ion battery and the electric double layer capacitor, has higher power density than the lithium ion battery and higher energy density than the electric double layer capacitor, and can maintain good power and cycle performance.
The lithium ion capacitor generally adopts a porous material as the anode, and the cathode generally adopts a lithium ion battery cathode material, so that the energy density attenuation speed of the lithium ion capacitor is high, and the use effect of the capacitor is influenced.
Disclosure of Invention
The invention aims to provide an all-fiber lithium ion capacitor and a preparation method thereof, and the all-fiber lithium ion capacitor provided by the invention has high energy density retention rate, and the energy density retention rate is still maintained at about 80% after 6000 cycles.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides an all-fiber lithium ion capacitor, which comprises a positive electrode, a diaphragm, a negative electrode and electrolyte;
the positive electrode is activated carbon-aramid fiber paper, and the thickness of the activated carbon-aramid fiber paper is 0.03-0.5 mm; the activated carbon-aramid fiber paper has pores;
the negative electrode is pre-lithiated carbon nanotube-aramid fiber paper, and the thickness of the pre-lithiated carbon nanotube-aramid fiber paper is 0.02-0.3 mm; the carbon nanotube-aramid fiber paper has pores.
Preferably, the preparation raw materials of the activated carbon-aramid fiber paper comprise the following components in parts by mass: 1 part of activated carbon, 0.1-0.3 part of carbon black, 0.5-1 part of aramid chopped fiber, 0.5-1 part of aramid pulp fiber, 0.025-0.05 part of defibering agent, 0.025-0.05 part of dispersing agent, 300-400 parts of water and 50-100 parts of ethanol.
Preferably, the preparation raw materials of the carbon nanotube-aramid fiber paper comprise the following components in parts by mass: 1 part of carbon nano tube, 0.3-0.8 part of aramid chopped fiber, 0.3-0.8 part of aramid pulp fiber, 0.015-0.04 part of defibering agent, 0.03-0.08 part of dispersing agent, 200-300 parts of water and 50-100 parts of ethanol.
Preferably, the diameter of the aramid chopped fiber is 5-15 mu m, and the length of the aramid chopped fiber is 3-5 mm.
The length of the aramid pulp fiber is 0.5-1.8 mm.
Preferably, the defibering agent comprises sodium dodecyl benzene sulfonate.
Preferably, the dispersant comprises polyethylene oxide.
Preferably, the diameter of the carbon nano tube is 30-150 nm, and the length of the carbon nano tube is 3-10 mu m.
The invention provides a preparation method of the all-fiber lithium ion capacitor, which comprises the following steps:
providing activated carbon-aramid fiber paper and pre-lithiated carbon nanotube-aramid fiber paper;
and assembling the activated carbon-aramid fiber paper with a diaphragm, the pre-lithiated carbon nanotube-aramid fiber paper and an electrolyte to obtain the all-fiber lithium ion capacitor.
Preferably, the preparation method of the activated carbon-aramid fiber paper comprises the following steps:
(1) mixing the aramid chopped fibers, a defibering agent and part of water, and sequentially defibering and pulping to obtain aramid chopped fiber pulp;
beating the mixture of aramid pulp fiber, a dispersing agent and the residual water to obtain aramid pulp fiber slurry;
(2) mixing the aramid chopped fiber pulp and the aramid pulp fiber pulp obtained in the step (1) with activated carbon, carbon black and ethanol, and shearing the obtained mixture to obtain mixed pulp;
(3) and (3) sequentially carrying out freeze drying and roll forming on the mixed slurry obtained in the step (2) to obtain the activated carbon-aramid fiber paper.
Preferably, the preparation method of the pre-lithiated carbon nanotube-aramid fiber paper comprises the following steps:
(a) mixing the aramid chopped fibers, a defibering agent and part of water, and sequentially defibering and pulping to obtain aramid chopped fiber pulp;
beating the mixture of aramid pulp fiber, a dispersing agent and the residual water to obtain aramid pulp fiber slurry;
mixing the carbon nano tube, a dispersing agent and ethanol to obtain carbon nano tube alcohol dispersion liquid;
(b) mixing the aramid chopped fiber slurry, the aramid pulp fiber slurry and the carbon nano tube alcohol dispersion liquid obtained in the step (a), and then sequentially shearing and grinding the obtained mixture to obtain mixed slurry;
(c) coating the mixed slurry obtained in the step (b) on a base material, drying, stripping the base material, and then carrying out hot press molding to obtain carbon nanotube-aramid fiber paper;
(d) and (c) carrying out pre-lithiation treatment on the carbon nanotube-aramid fiber paper obtained in the step (c) to obtain pre-lithiated carbon nanotube-aramid fiber paper.
The invention provides an all-fiber lithium ion capacitor, which comprises a positive electrode, a diaphragm, a negative electrode and electrolyte; the positive electrode is activated carbon-aramid fiber paper, and the thickness of the activated carbon-aramid fiber paper is 0.03-0.5 mm; the activated carbon-aramid fiber paper has pores; the negative electrode is pre-lithiated carbon nanotube-aramid fiber paper, and the thickness of the pre-lithiated carbon nanotube-aramid fiber paper is 0.02-0.3 mm; the carbon nanotube-aramid fiber paper has pores. The active carbon-aramid fiber paper is used as the anode, and the anode material is ensured to have higher strength within the thickness range; meanwhile, the activated carbon-aramid fiber paper has high conductivity and large specific surface area, and can greatly improve the adsorption and desorption amount of lithium ions, so that the energy density of the lithium ion capacitor is improved; the carbon nanotube-aramid fiber paper subjected to pre-lithiation is used as a negative electrode, the negative electrode material has excellent strength performance within the thickness range, meanwhile, the pore structure of the carbon nanotube-aramid fiber paper can greatly improve the insertion and extraction capacity of lithium ions, the power density of the capacitor is effectively improved, the pre-lithiation layer enables the negative electrode to tend to a lower and more stable voltage platform, the active carbon positive electrode is ensured to work within a more stable working voltage range, the active carbon electrode is fully utilized, and the energy density of the capacitor is improved. In addition, the all-fiber lithium ion capacitor provided by the invention uses aramid fiber as a framework, and the high strength and the good corrosion resistance of the all-fiber lithium ion capacitor can greatly improve the cycle stability of the lithium ion capacitor.
The example result shows that when the current density is 100mA/g, the discharge energy density of the all-fiber lithium ion capacitor provided by the invention is 94.5Wh/g, and when the current density is 1500mA/g, the discharge energy density reaches 72 Wh/g; the energy density retention rate of the alloy is about 80 percent after being cycled 6000 times under the current density of 100 mA/g.
Drawings
FIG. 1 shows the results of testing the constant current charge/discharge performance of the all-fiber lithium ion capacitor obtained in example 1 at 100 mA/g;
FIG. 2 shows the results of the constant current charge/discharge performance test of the all-fiber type lithium ion capacitor obtained in example 1 at 1500 mA/g;
FIG. 3 is a graph showing the cycle number-energy density retention rate relationship of the all-fiber type lithium ion capacitor obtained in example 1 in a cycle test at 100 mA/g.
Detailed Description
The invention provides an all-fiber lithium ion capacitor, which comprises a positive electrode, a diaphragm, a negative electrode and electrolyte;
the positive electrode is activated carbon-aramid fiber paper, and the thickness of the activated carbon-aramid fiber paper is 0.03-0.5 mm; the activated carbon-aramid fiber paper has pores;
the negative electrode is pre-lithiated carbon nanotube-aramid fiber paper, and the thickness of the pre-lithiated carbon nanotube-aramid fiber paper is 0.02-0.3 mm; the carbon nanotube-aramid fiber paper has pores.
The all-fiber lithium ion capacitor provided by the invention comprises a positive electrode, wherein the positive electrode is activated carbon-aramid fiber paper, and the thickness of the activated carbon-aramid fiber paper is 0.03-0.5 mm, preferably 0.05-0.4 mm, and more preferably 0.1-0.3 mm; the activated carbon-aramid fiber paper is provided with pores, and the pore diameter of the pores is preferably 2-100 nm; the above pore size parameters refer to the minimum and maximum values of pore size in the material. In the invention, the specific surface area of the activated carbon-aramid fiber paper is preferably 600-1000 m2(iv)/g, more preferably 610 to 950m2/g。
In the invention, the preparation raw materials of the activated carbon-aramid fiber paper preferably comprise the following components in parts by mass: 1 part of activated carbon, 0.1-0.3 part of carbon black, 0.5-1 part of aramid chopped fiber, 0.5-1 part of aramid pulp fiber, 0.025-0.05 part of defibering agent, 0.025-0.05 part of dispersing agent, 300-400 parts of water and 50-100 parts of ethanol.
The preparation raw material of the activated carbon-aramid fiber paper preferably comprises 1 part by mass of activated carbon. The activated carbon of the present invention has no particular requirement, and may be a commercially available product well known to those skilled in the art.
The preparation raw material of the activated carbon-aramid fiber paper preferably comprises 0.1-0.3 part of carbon black, more preferably 0.15-0.25 part of carbon black, and even more preferably 0.18-0.23 part of carbon black based on 1 part by mass of the activated carbon. In the present invention, the carbon black is preferably a conductive super carbon black. The source of the carbon black is not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used.
The preparation raw material of the activated carbon-aramid fiber paper preferably comprises 0.5-1 part of aramid chopped fiber, more preferably 0.06-0.09 part of aramid chopped fiber, and even more preferably 0.07-0.08 part of aramid chopped fiber based on 1 part by mass of the activated carbon. In the invention, the diameter of the aramid chopped fiber is preferably 5-15 μm, more preferably 6-14 μm, and further preferably 8-12 μm; the length is preferably 3 to 5mm, more preferably 3.2 to 4.8mm, and still more preferably 3.5 to 4.5 mm.
The preparation raw material of the activated carbon-aramid fiber paper preferably comprises 0.5-1 part of aramid pulp fiber, more preferably 0.6-0.9 part of aramid pulp fiber, and even more preferably 0.7-0.8 part of aramid pulp fiber based on 1 part by mass of the activated carbon. In the invention, the length of the aramid pulp fiber is preferably 0.5-1.8 mm, more preferably 0.6-1.5 mm, and still more preferably 0.8-1.2 mm.
The preparation raw materials of the activated carbon-aramid fiber paper preferably comprise 0.015-0.04 part of defibering agent, more preferably 0.02-0.035 part of defibering agent, and even more preferably 0.02-0.03 part of defibering agent based on 1 part by mass of the activated carbon. In the present invention, the fluffing agent preferably comprises sodium dodecylbenzene sulfonate.
The preparation raw material of the activated carbon-aramid fiber paper preferably comprises 0.025-0.05 part by mass of a dispersing agent, more preferably 0.03-0.045 part by mass of the activated carbon, and even more preferably 0.035-0.04 part by mass of the activated carbon. In the present invention, the dispersant preferably includes polyethylene oxide.
The preparation raw material of the activated carbon-aramid fiber paper disclosed by the invention preferably comprises 300-400 parts of water, more preferably 320-380 parts of water, and further preferably 325-375 parts of water based on 1 part by mass of the activated carbon. In the present invention, the water is preferably deionized water.
The anode preparation raw material provided by the invention further comprises 50-100 parts of ethanol, more preferably 60-90 parts of ethanol, and even more preferably 70-85 parts of ethanol based on 1 part by mass of the activated carbon. In the present invention, the ethanol is preferably anhydrous ethanol.
The invention preferably takes the activated carbon, the carbon black, the aramid chopped fiber, the aramid pulp fiber, the defibering agent, the dispersing agent, the water and the ethanol in parts by mass as the preparation raw materials, and can form the positive electrode material which takes the aramid chopped fiber and the aramid pulp fiber as the framework structure, has the activated carbon uniformly dispersed in the network framework structure, has a pore structure and has higher strength. In the invention, the tensile strength of the activated carbon-aramid fiber paper is preferably 2.0-3.5 kg/mm2More preferably 2.3 to 3.3kg/mm2。
The all-fiber lithium ion capacitor provided by the invention comprises a diaphragm, wherein the diaphragm is preferably a polyimide nanofiber diaphragm, and the porosity of the diaphragm is preferably 60-80%, more preferably 65-75%; the thickness of the diaphragm is preferably 30 to 50 μm, and more preferably 35 to 45 μm.
The all-fiber lithium ion capacitor provided by the invention comprises a negative electrode, wherein the negative electrode is pre-lithiated carbon nanotube-aramid fiber paper, and the thickness of the pre-lithiated carbon nanotube-aramid fiber paper is 0.02-0.3 mm, preferably 0.05-0.25 mm, and more preferably 0.07-0.2 mm; the carbon nanotube-aramid fiber paper is provided with pores, and the pore diameter of the pores is preferably 2-110 nm; the above pore size parameters refer to the minimum and maximum values of pore size in the material. The specific surface area of the carbon nanotube-aramid fiber paper is preferably 30-40 m2(iv)/g, more preferably 34 to 37m2/g。
In the invention, the pre-lithiated carbon nanotube-aramid fiber paper refers to a composite material in which a lithium layer is compounded on the surface of the carbon nanotube-aramid fiber paper. The method of the lithium layer recombination is described later. In the invention, the preparation raw materials of the carbon nanotube-aramid fiber paper preferably comprise the following components in parts by mass: 1 part of carbon nano tube, 0.3-0.8 part of aramid chopped fiber, 0.3-0.8 part of aramid pulp fiber, 0.015-0.04 part of defibering agent, 0.03-0.08 part of dispersing agent, 200-300 parts of water and 50-100 parts of ethanol.
The preparation raw material of the carbon nanotube-aramid fiber paper comprises 1 part of the preferred carbon nanotube by mass. In the invention, the diameter of the carbon nano tube is preferably 30-150 nm, and more preferably 45-140 nm; the length is preferably 3 to 10 μm, and more preferably 48 μm. The carbon nanotube of the present invention is preferably a multi-walled carbon nanotube.
The preparation raw material of the carbon nanotube-aramid fiber paper preferably comprises 0.3-0.8 part of aramid chopped fiber, more preferably 0.4-0.7 part of aramid chopped fiber, and even more preferably 0.5-0.6 part of aramid chopped fiber based on 1 part by mass of the carbon nanotube. In the present invention, the diameter and length of the aramid chopped fiber are preferably in accordance with the selection range of the diameter and length of the aramid chopped fiber in the raw material for preparing the activated carbon-aramid fiber paper described in the above technical means, and are not repeated here.
The preparation raw material of the carbon nanotube-aramid fiber paper preferably comprises 0.3-0.8 part of aramid pulp fiber, more preferably 0.4-0.7 part of aramid pulp fiber, and even more preferably 0.5-0.6 part of aramid pulp fiber based on 1 part by mass of the carbon nanotube. In the invention, the length of the aramid pulp fiber is preferably consistent with the length selection range of the aramid pulp fiber in the raw material for preparing the activated carbon-aramid fiber paper in the technical scheme, and the selection range is not repeated here.
The preparation raw materials of the carbon nanotube-aramid fiber paper preferably comprise 0.015-0.4 part of defibering agent, more preferably 0.02-0.035 part of defibering agent, and even more preferably 0.025-0.3 part of defibering agent based on 1 part by mass of the carbon nanotube. In the present invention, the fluffing agent preferably comprises sodium dodecylbenzene sulfonate.
The preparation raw material of the carbon nanotube-aramid fiber paper preferably comprises 0.03-0.08 part of dispersant, more preferably 0.04-0.07 part of dispersant, and even more preferably 0.05-0.06 part of dispersant based on 1 part by mass of the carbon nanotube. In the present invention, the dispersant preferably includes polyethylene oxide.
The preparation raw material of the carbon nanotube-aramid fiber paper disclosed by the invention preferably comprises 200-300 parts of water, more preferably 210-290 parts of water, and even more preferably 215-285 parts of water based on 1 part by mass of the carbon nanotube. In the present invention, the water is preferably deionized water.
The preparation raw material of the carbon nanotube-aramid fiber paper disclosed by the invention also comprises 50-100 parts of ethanol, more preferably 60-90 parts of ethanol, and even more preferably 70-80 parts of ethanol based on 1 part by mass of the carbon nanotube. In the present invention, the ethanol is preferably anhydrous ethanol.
According to the invention, the carbon nano tube, the aramid chopped fiber, the aramid pulp fiber, the defibering agent, the dispersing agent, the water and the ethanol are preferably used as raw materials in the above dosage, so that the negative electrode material with a porous structure and higher strength can be obtained, and the method is favorable for improving the cycle performance of the lithium ion capacitor. In the invention, the tensile strength of the carbon nano tube-aramid fiber paper is 3.0-3.5 kg/mm2More preferably 3.1 to 3.4kg/mm2。
The invention takes the carbon nano tube-aramid fiber paper pre-lithiated as the negative electrode, can greatly improve the lithium intercalation dynamics, can be competent for the charge-discharge work of the lithium ion capacitor under the heavy current density, and has good charge-discharge multiplying power performance.
The all-fiber lithium ion capacitor provided by the invention comprises an electrolyte, wherein the electrolyte is preferably LiPF6And (3) an electrolyte. The concentration of the electrolyte is not particularly required in the present invention, and those skilled in the art can use the electrolyte.
The all-fiber lithium ion capacitor provided by the invention preferably further comprises a positive electrode shell and a negative electrode shell. The present invention has no special requirements on the composition of the positive electrode can and the negative electrode can, and the method is well known to those skilled in the art.
The components referred to in the above embodiments are, unless otherwise specified, commercially available products well known to those skilled in the art.
The invention provides a preparation method of the all-fiber lithium ion capacitor in the technical scheme, which comprises the following steps:
providing activated carbon-aramid fiber paper and pre-lithiated carbon nanotube-aramid fiber paper;
and assembling the activated carbon-aramid fiber paper with a diaphragm, the pre-lithiated carbon nanotube-aramid fiber paper and an electrolyte to obtain the all-fiber lithium ion capacitor.
In the present invention, the preparation method of the activated carbon-aramid fiber paper preferably includes:
(1) mixing the aramid chopped fibers, a defibering agent and part of water, and sequentially defibering and pulping to obtain aramid chopped fiber pulp;
beating the mixture of aramid pulp fiber, a dispersing agent and the residual water to obtain aramid pulp fiber slurry;
(2) mixing the aramid chopped fiber pulp and the aramid pulp fiber pulp obtained in the step (1) with activated carbon, carbon black and ethanol, and shearing the obtained mixture to obtain mixed pulp;
(3) sequentially carrying out freeze drying and roll forming on the mixed slurry obtained in the step (2) to obtain activated carbon-aramid fiber paper;
(4) and (4) assembling the activated carbon-aramid fiber paper obtained in the step (3) with a diaphragm, a negative electrode and electrolyte to obtain the all-fiber type ionic capacitor.
According to the invention, the aramid chopped fibers, the defibering agent and part of water are preferably mixed, and sequentially subjected to defibering and pulping to obtain the aramid chopped fiber pulp. In the present invention, the part of the water is derived from the water in the raw material for preparing the positive electrode. The invention has no special requirement on the dosage of the water, and the aramid chopped fiber and the defibering agent can be uniformly dispersed. In the invention, the preferable mode of the fluffing is standing, and the preferable time of the fluffing is 5-15 min, and more preferably 8-12 min; the preferable temperature of the defibering is 30-60 ℃, and the more preferable temperature is 40-60 ℃; the power during pulping is preferably 300-1000W, more preferably 500-800W; the beating time is preferably 5-10 min, and more preferably 6-8 min.
According to the invention, the mixture of the aramid pulp fiber, the dispersing agent and the residual water is preferably pulped to obtain the aramid pulp fiber slurry. In the invention, the residual water is water in the cathode preparation raw material, and the sum of the residual water and the part of water is consistent with the amount of water in the cathode preparation raw material. In the invention, the shearing speed is preferably 2000-3000 r/min, more preferably 2200-2500 r/min; the shearing time is preferably 30-60 min, and more preferably 40-50 min.
In the invention, the preparation processes of the aramid chopped fiber pulp and the aramid pulp fiber pulp are not divided in sequence.
After the aramid chopped fiber pulp and the aramid pulp fiber pulp are obtained, the aramid chopped fiber pulp and the aramid pulp fiber pulp are preferably mixed with activated carbon, carbon black and ethanol, and then the obtained mixture is sheared to obtain mixed pulp.
The present invention does not require special means for such mixing, and may be practiced in a manner well known to those skilled in the art. In the present invention, the mixing preferably comprises: mixing activated carbon, carbon black and ethanol to obtain an alcohol dispersion liquid; and then mixing the alcohol dispersion liquid with the aramid chopped fiber slurry and the aramid pulp fiber slurry.
In the invention, when the mixture is sheared, the shearing speed is preferably 2000-3000 r/min, and more preferably 2200-2500 r/min; the shearing time is preferably 30-60 min, and more preferably 40-50 min.
After the mixed slurry is obtained, the mixed slurry is preferably subjected to freeze drying and roll forming in sequence to obtain the activated carbon-aramid fiber paper. In the present invention, the temperature of the freeze-drying is preferably-15 to-25 ℃, more preferably-18 to-23 ℃, and still more preferably-20 ℃; the freeze drying time is preferably 15-20 h, and more preferably 16-18 h. In the invention, the pressure is preferably 10-20 kN/m, more preferably 12-18 kN/m, and still more preferably 14-16 kN/m during roll forming; the number of rolling is preferably 3 to 5, more preferably 3 to 4.
In the present invention, the method for preparing the pre-lithiated carbon nanotube-aramid fiber paper preferably includes:
(a) mixing the aramid chopped fibers, a defibering agent and part of water, and sequentially defibering and pulping to obtain aramid chopped fiber pulp;
beating the mixture of aramid pulp fiber, a dispersing agent and the residual water to obtain aramid pulp fiber slurry;
mixing the carbon nano tube, a dispersing agent and ethanol to obtain carbon nano tube alcohol dispersion liquid;
(b) mixing the aramid chopped fiber slurry, the aramid pulp fiber slurry and the carbon nano tube alcohol dispersion liquid obtained in the step (a), and then sequentially shearing and grinding the obtained mixture to obtain mixed slurry;
(c) coating the mixed slurry obtained in the step (b) on a base material, drying, stripping the base material, and then carrying out hot press molding to obtain carbon nanotube-aramid fiber paper;
(d) and (c) carrying out pre-lithiation treatment on the carbon nanotube-aramid fiber paper obtained in the step (c) to obtain pre-lithiated carbon nanotube-aramid fiber paper.
In the invention, in the process of preparing the carbon nanotube-aramid fiber paper, the preparation methods of the aramid chopped fiber pulp and the aramid pulp fiber pulp are preferably consistent with the corresponding scheme when the activated carbon-aramid fiber paper is provided in the technical scheme, and are not repeated here.
In the present invention, the carbon nanotube dispersion liquid is preferably prepared by a method well known to those skilled in the art, and the carbon nanotube and the dispersant can be uniformly dispersed in ethanol.
In the invention, the preparation sequence of the aramid chopped fiber pulp, the aramid pulp fiber pulp and the carbon nano tube alcohol dispersion liquid is not divided in sequence.
After the aramid chopped fiber pulp, the aramid pulp fiber pulp and the carbon nanotube alcohol dispersion liquid are obtained, the aramid chopped fiber pulp, the aramid pulp fiber pulp and the carbon nanotube alcohol dispersion liquid are preferably mixed, and then the obtained mixture is sequentially sheared and ground to obtain the mixed pulp. In the invention, the shearing speed is preferably 2000-3000 r/min, more preferably 2200-2500 r/min; the shearing time is preferably 30-60 min, and more preferably 40-50 min; the grinding time is preferably 15 to 40min, and more preferably 20 to 30 min. In the present invention, the grinding is preferably carried out in a sand mill.
After the mixed slurry is obtained, the mixed slurry is preferably coated on a base material, the base material is peeled after being dried, and then the carbon nanotube-aramid fiber paper is obtained through hot press molding. The present invention does not require special means for said coating, and may be carried out in a manner known to the person skilled in the art. In the embodiment of the present invention, the coating is preferably performed by brushing. In the present invention, the substrate preferably includes a copper foil or an aluminum foil. In the invention, the dosage of the mixed slurry is preferably 0.05-0.1 g/cm during coating2More preferably 0.06 to 0.08g/cm2(ii) a The drying temperature is preferably 50-80 ℃, and more preferably 60-70 ℃; the drying time is preferably 3-8 h, and more preferably 5-7 h. The invention has no special requirement on the specific stripping mode, and the formed film material can be separated from the base material. In the invention, the hot-press forming temperature is preferably 180-230 ℃, and more preferably 200-220 ℃; the pressure is preferably 8-13 MPa, and more preferably 9-11 MPa; the time is preferably 3 to 10min, and more preferably 4 to 8 min.
After the carbon nanotube-aramid fiber paper is obtained, the carbon nanotube-aramid fiber paper is preferably subjected to pre-lithiation treatment to obtain the pre-lithiated carbon nanotube-aramid fiber paper. In the present invention, the prelithiation is preferably performed by pulse charging.
In the present invention, the pulse charging prelithiation mode is specifically preferably: in a three-electrode system, carbon nanotube-aramid fiber paper is used as a working electrode, a lithium sheet is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and LiPF (lithium ion PF)6And as an electrolyte, finishing the pre-lithiation treatment of the negative electrode by a pulse charging mode.
In the present invention, the manner of the pulse charging prelithiation is more preferably: the charging is carried out by pulse current of 0.1C, each pulse is charged for 30-60 min, more preferably 40-50 min, and the relaxation time is 30 min. The whole pulse charging time is preferably 8-12 h, and more preferably 9-10 h. In the present invention, the pulse time is a charge time, and the relaxation time is a stop charge time.
After the activated carbon-aramid fiber paper and the pre-lithiated carbon nanotube-aramid fiber paper are provided, the activated carbon-aramid fiber paper and the pre-lithiated carbon nanotube-aramid fiber paper are assembled with a diaphragm and an electrolyte to obtain the all-fiber lithium ion capacitor.
The present invention does not require any particular embodiment of the assembly, and the assembly may be performed by using the order of the positive electrode, the separator, the negative electrode and the electrolyte, which is well known to those skilled in the art.
In the present invention, when the all-fiber lithium ion capacitor preferably further includes a positive electrode can and a negative electrode can, the assembly is preferably performed in the form of the positive electrode can, the positive electrode, the separator, the negative electrode can, and the electrolyte.
In order to further illustrate the present invention, the following describes in detail the all-fiber type lithium ion capacitor and the preparation method thereof provided by the present invention with reference to the drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of activated carbon-aramid fiber paper (positive electrode):
weighing 1.5g of aramid chopped fibers and 0.075g of sodium dodecyl benzene sulfonate in 450g of aqueous solution, standing and soaking for 20min, washing for several times, and pulping for 10min by using a pulping machine to obtain the aramid chopped fiber slurry.
Weighing 1.5g of aramid pulp fiber and 0.075g of polyethylene oxide in 450g of aqueous solution, and stirring for 5min to obtain aramid pulp fiber slurry.
3g (1 part) of activated carbon and 0.3g of conductive super carbon black are weighed and dispersed in ethanol, and are uniformly mixed with the prepared aramid chopped fiber pulp and aramid pulp fiber pulp, and then are sheared for 30min at the speed of 2000r/min to obtain mixed pulp.
And (3) freeze-drying the prepared mixed slurry at the temperature of-20 ℃ for 18h, and then rolling for 3 times under the pressure of 15kN/m to form the activated carbon-aramid fiber paper.
Preparing carbon nanotube-aramid fiber paper:
weighing 1.5g of aramid chopped fibers and 0.045g of sodium dodecyl benzene sulfonate in 300g of aqueous solution, standing and soaking for 20min, washing for a plurality of times, and pulping for 10min by using a pulping machine to obtain the aramid chopped fiber slurry.
Weighing 1.5g of aramid pulp fiber and 0.09g of polyethylene oxide in 300g of aqueous solution, and stirring for 5min to obtain aramid pulp fiber slurry.
Weighing 3g (1 part) of carbon nanotube and 0.03g of SDS, dispersing in 150g of ethanol, carrying out ultrasonic treatment for 30min, carrying out high-speed shearing for 30min, uniformly mixing the obtained carbon nanotube dispersion liquid with the prepared aramid chopped fiber slurry and aramid pulp fiber slurry, shearing for 30min by using a high-speed shearing machine, grinding for 1h by using a sand mill, coating the slurry on a foil substrate by using a slit extrusion coating mode, drying, stripping the substrate, and carrying out hot press molding to obtain the carbon nanotube-aramid fiber paper.
Under a three-electrode system, carbon nano tube-aramid fiber paper is used as a working electrode, a lithium sheet is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and LiPF (lithium ion PF)6As an electrolyte, the negative electrode pre-lithiation treatment is completed in a pulse charging mode, wherein the pulse charging parameters are as follows: charging is carried out at 0.1C pulse current, each pulse is charged for 60min, and the relaxation time is 30 min. The whole pulse charging time is 12 h. And obtaining the pre-lithiated carbon nanotube-aramid fiber paper after the pulse is finished.
And (3) operating according to the sequence of the positive electrode shell, the positive electrode, the diaphragm (cellulose diaphragm), the pre-lithiated negative electrode, the negative electrode shell and the dropwise adding of the electrolyte to obtain the all-fiber lithium ion capacitor.
Examples 2 to 3
An all-fiber type lithium ion capacitor was prepared in the same manner as in example 1, except that the amounts of the raw materials for preparing the positive electrode and the negative electrode were different, as shown in table 1.
Table 1 examples 1 to 3 amounts of raw materials for preparing positive and negative electrodes
Figure GDA0002572286380000121
Structure, Performance characterization and results
Testing the thickness, specific surface area and pore diameter of the obtained activated carbon-aramid fiber paper and pre-lithiated carbon nanotube-aramid fiber paper by using a specific surface area analyzer;
testing the surface resistance of the obtained activated carbon-aramid fiber paper and the pre-lithiated carbon nanotube-aramid fiber paper by using a four-probe resistance meter;
the tensile strength of the obtained activated carbon-aramid fiber paper and the pre-lithiated carbon nanotube-aramid fiber paper was measured by a method of hanging weights under a unit cross-sectional area, and the test results are listed in table 2.
Table 2 results of performance test of activated carbon-aramid fiber paper and carbon nanotube-aramid fiber paper obtained in examples 1 to 3
Figure GDA0002572286380000131
The all-fiber lithium ion capacitors obtained in examples 1 to 3 were subjected to constant current charge and discharge tests with a novacar cell test cabinet, wherein the charge and discharge voltage window was 2.2 to 4V, the charge and discharge current densities were 100mA/g and 1500mA/g, respectively, and the test results of example 1 are shown in fig. 1 and 2. As can be seen from FIG. 1, when the current density was 100mA/g, the discharge energy density was 94.5 Wh/g; as can be seen from FIG. 2, when the current density was 1500mA/g, the discharge energy density reached 72Wh/g, showing good rate capability. In addition, the rising curve in fig. 2 is a charging curve, the falling curve is a discharging curve, the platform is a constant-voltage pressure maintaining part, and the charging curve and the discharging curve form a good isosceles triangle shape according to the curve variation trend, so that the good capacitance characteristic is represented. Examples 2 and 3 have similar performance test results as example 1.
The test results of example 1 are shown in FIG. 3, which shows that the cycle number-energy density retention rate relationship curve is obtained by 6000 cycles at a current density of 100 mA/g. As can be seen from FIG. 3, the energy density retention rate can still reach 82% even after 6000 cycles of the capacitor are performed at a current density of 100mA/g, and good capacitor performance is shown. Examples 2 and 3 have similar test results as example 1.
According to the embodiment, the all-fiber lithium ion capacitor provided by the invention has the advantages of good rate performance and cycle stability, and longer service life.
The preparation raw materials of the anode and the cathode of the lithium ion capacitor provided by the invention use a large amount of fiber materials, so that the raw material cost of the lithium ion capacitor is reduced.
The preparation method of the lithium ion capacitor provided by the invention is simple, has high operability and is suitable for large-scale production.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.

Claims (6)

1. An all-fiber lithium ion capacitor comprises a positive electrode, a diaphragm, a negative electrode and electrolyte; the positive electrode is made of activated carbon-aramid fiber paper, and the thickness of the activated carbon-aramid fiber paper is 0.03-0.5 mm; the activated carbon-aramid fiber paper has pores;
the preparation raw materials of the activated carbon-aramid fiber paper comprise the following components in parts by mass: 1 part of activated carbon, 0.1-0.3 part of carbon black, 0.5-1 part of aramid chopped fiber, 0.5-1 part of aramid pulp fiber, 0.025-0.05 part of defibering agent, 0.025-0.05 part of dispersing agent, 300-400 parts of water and 50-100 parts of ethanol;
the preparation method of the activated carbon-aramid fiber paper comprises the following steps:
(1) mixing the aramid chopped fibers, a defibering agent and part of water, and sequentially defibering and pulping to obtain aramid chopped fiber pulp;
beating the mixture of aramid pulp fiber, a dispersing agent and the residual water to obtain aramid pulp fiber slurry;
(2) mixing the aramid chopped fiber pulp and the aramid pulp fiber pulp obtained in the step (1) with activated carbon, carbon black and ethanol, and shearing the obtained mixture to obtain mixed pulp;
(3) sequentially carrying out freeze drying and roll forming on the mixed slurry obtained in the step (2) to obtain activated carbon-aramid fiber paper;
the negative electrode is pre-lithiated carbon nanotube-aramid fiber paper, and the thickness of the pre-lithiated carbon nanotube-aramid fiber paper is 0.02-0.3 mm; the carbon nano tube-aramid fiber paper is provided with pores;
the preparation raw materials of the carbon nanotube-aramid fiber paper comprise the following components in parts by mass: 1 part of carbon nano tube, 0.3-0.8 part of aramid chopped fiber, 0.3-0.8 part of aramid pulp fiber, 0.015-0.04 part of defibering agent, 0.03-0.08 part of dispersing agent, 200-300 parts of water and 50-100 parts of ethanol;
the preparation method of the pre-lithiated carbon nanotube-aramid fiber paper comprises the following steps:
(a) mixing the aramid chopped fibers, a defibering agent and part of water, and sequentially defibering and pulping to obtain aramid chopped fiber pulp;
mixing the carbon nano tube, a dispersing agent and ethanol to obtain carbon nano tube alcohol dispersion liquid;
(b) mixing the aramid chopped fiber slurry, the aramid pulp fiber slurry and the carbon nano tube alcohol dispersion liquid obtained in the step (a), and then sequentially shearing and grinding the obtained mixture to obtain mixed slurry;
(c) coating the mixed slurry obtained in the step (b) on a base material, drying, stripping the base material, and then carrying out hot press molding to obtain carbon nanotube-aramid fiber paper;
(d) and (c) carrying out pre-lithiation treatment on the carbon nanotube-aramid fiber paper obtained in the step (c) to obtain pre-lithiated carbon nanotube-aramid fiber paper.
2. The all-fiber lithium ion capacitor according to claim 1, wherein the aramid chopped fiber has a diameter of 5 to 15 μm and a length of 3 to 5 mm;
the length of the aramid pulp fiber is 0.5-1.8 mm.
3. The all-fiber lithium ion capacitor according to claim 1, wherein the fluffing agent comprises sodium dodecylbenzene sulfonate.
4. The all-fiber lithium ion capacitor according to claim 1, wherein the dispersant comprises polyethylene oxide.
5. The all-fiber lithium ion capacitor according to claim 1, wherein the carbon nanotubes have a diameter of 30 to 150nm and a length of 3 to 10 μm.
6. The method for preparing the all-fiber lithium ion capacitor according to any one of claims 1 to 5, comprising the steps of:
providing activated carbon-aramid fiber paper and pre-lithiated carbon nanotube-aramid fiber paper;
assembling the activated carbon-aramid fiber paper with a diaphragm, pre-lithiated carbon nanotube-aramid fiber paper and an electrolyte to obtain a full-fiber type lithium ion capacitor;
the preparation method of the activated carbon-aramid fiber paper comprises the following steps:
(1) mixing the aramid chopped fibers, a defibering agent and part of water, and sequentially defibering and pulping to obtain aramid chopped fiber pulp;
beating the mixture of aramid pulp fiber, a dispersing agent and the residual water to obtain aramid pulp fiber slurry;
(2) mixing the aramid chopped fiber pulp and the aramid pulp fiber pulp obtained in the step (1) with activated carbon, carbon black and ethanol, and shearing the obtained mixture to obtain mixed pulp;
(3) sequentially carrying out freeze drying and roll forming on the mixed slurry obtained in the step (2) to obtain activated carbon-aramid fiber paper;
the preparation method of the pre-lithiated carbon nanotube-aramid fiber paper comprises the following steps:
(a) mixing the aramid chopped fibers, a defibering agent and part of water, and sequentially defibering and pulping to obtain aramid chopped fiber pulp;
mixing the carbon nano tube, a dispersing agent and ethanol to obtain carbon nano tube alcohol dispersion liquid;
(b) mixing the aramid chopped fiber slurry, the aramid pulp fiber slurry and the carbon nano tube alcohol dispersion liquid obtained in the step (a), and then sequentially shearing and grinding the obtained mixture to obtain mixed slurry;
(c) coating the mixed slurry obtained in the step (b) on a base material, drying, stripping the base material, and then carrying out hot press molding to obtain carbon nanotube-aramid fiber paper;
(d) and (c) carrying out pre-lithiation treatment on the carbon nanotube-aramid fiber paper obtained in the step (c) to obtain pre-lithiated carbon nanotube-aramid fiber paper.
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CN106373788A (en) * 2016-11-14 2017-02-01 南昌大学 Lithium ion super capacitor pre-embedded lithium pole sheet manufacture method
CN108755279A (en) * 2018-07-06 2018-11-06 江西克莱威纳米碳材料有限公司 A kind of aramid fiber porous, electrically conductive paper and preparation method thereof
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