CN111799431A - Nanoscale hole material, electrode and energy storage equipment - Google Patents

Nanoscale hole material, electrode and energy storage equipment Download PDF

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Publication number
CN111799431A
CN111799431A CN201910277053.0A CN201910277053A CN111799431A CN 111799431 A CN111799431 A CN 111799431A CN 201910277053 A CN201910277053 A CN 201910277053A CN 111799431 A CN111799431 A CN 111799431A
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nanoscale
pore
hole
electrode
equal
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辛民昌
李长明
吴超
辛程勋
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Qingdao Jiuhuan Xinyue New Energy Technology Co ltd
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Qingdao Jiuhuan Xinyue New Energy Technology Co ltd
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

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  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a nanoscale hole material which comprises a material body, wherein at least one side surface of the material body is provided with a nanoscale hole. The invention also discloses an electrode which comprises a base material, wherein the nano-scale pore material is arranged on at least one side surface of the two side surfaces of the base material. The invention also discloses energy storage equipment, which comprises an electronically insulated diaphragm capable of passing ions, wherein electrodes are respectively arranged on two sides of the diaphragm, and the electrodes are the electrodes. According to the nanoscale pore material disclosed by the invention, the nanoscale pores are arranged on the side surface of the material body, so that the specific surface area can be increased, and when the nanoscale pore material is used on an electrode and energy storage equipment, electrolyte can be transmitted in the nanoscale pores, so that the specific surface area of the electrode is increased, the interior of the electrode can participate in charging and discharging, the specific power of the energy storage equipment is increased, and the utilization rate of a porous electrode is greatly increased.

Description

Nanoscale hole material, electrode and energy storage equipment
Technical Field
The invention relates to a nanoscale pore material, in particular to a nanoscale pore material, and an electrode and energy storage equipment which are made of the nanoscale pore material.
Background
The conventional lithium ion battery includes a positive electrode, a negative electrode, and a separator, and an electrolyte is disposed between the positive electrode and the negative electrode. According to the charge-discharge principle of the lithium ion battery, the following characteristics are found: the charge and discharge process of the lithium ion battery is the process of lithium ion intercalation and deintercalation. When the battery is charged, lithium ions are generated on the positive electrode of the battery, and the generated lithium ions move to the negative electrode through the electrolyte. The carbon as the negative electrode has a layered structure having many pores, and lithium ions reaching the negative electrode are inserted into the pores of the carbon layer, and the more lithium ions are inserted, the higher the charge capacity is. Similarly, when the battery is discharged, lithium ions embedded in the carbon layer of the negative electrode are extracted and move back to the positive electrode. The more lithium ions returned to the positive electrode, the higher the discharge capacity. The lithium battery discharge needs to pay attention to several points: first, the discharge current cannot be excessive, and excessive current may cause heat generation inside the battery, resulting in permanent damage. Second, absolutely no over-discharge! The internal storage of electric energy in lithium batteries is realized by an electrochemical reversible chemical change, and an irreversible reaction of the chemical change can be caused by excessive discharge, so that the lithium batteries are most afraid of over-discharge and can possibly cause the rejection of the batteries once the discharge voltage is lower than 2.7V.
In the charging and discharging process of the lithium ion battery, only the surfaces of holes with certain depths of the positive electrode and the negative electrode are in contact with electrolyte to generate the insertion and the extraction of lithium ions, and the materials of the positive electrode and the negative electrode cannot completely participate in the insertion and the extraction of the lithium ions, which is also the reason for the small charging and discharging current of the existing lithium ion battery, not only limits the charging and discharging capacity of the lithium ion battery, but also limits the charging and discharging power of the battery.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a nanoscale pore material, an electrode and an energy storage device, which can effectively increase the specific surface area.
In order to achieve the purpose, the invention provides the following technical scheme:
a nanoscale pore material comprising a material body (1), regularly distributed nanoscale pores (2) on at least one side of the material body (1).
Further, the nanoscale hole (2) is a blind hole arranged on the side face of the material body (1).
Further, in two radial cross sections of any two planes perpendicular to the axis of the nanoscale hole (2) and cut on the nanoscale hole (2), the area of the radial cross section closer to the hole bottom of the nanoscale hole (2) is less than or equal to the area of the radial cross section farther from the hole bottom of the nanoscale hole (2).
Further, the nanoscale hole (2) is a through hole penetrating through the material body (1).
Further, two radial sections of any plane perpendicular to the axis of the nano-scale hole (2) on the nano-scale hole (2) are similar in graph.
Further, the radial section is circular, oval, triangular, square, rectangular, rhombic or regular polygonal.
Further, the nanoscale pores (2) are arranged in an array.
Further, the nanoscale holes (2) are arranged in a gradient array.
Further, the nanoscale holes (2) are arranged in a gradient array by taking the hole diameter, the hole interval or the hole shape as a reference.
Further, the pore diameter of the nanoscale pores (2) is greater than or equal to 1 nm.
Further, the aperture of the nanoscale hole (2) is less than or equal to 1 um.
Further, the pore diameter of the nanoscale pores (2) is less than or equal to 100 nm.
Further, the pore diameter of the nanoscale pores (2) is less than or equal to 50 nm.
Further, the pore diameter of the nanoscale pores (2) is greater than or equal to 2 nm.
Further, the inter-pore spacing between the nanoscale pores (2) is such that:
L≤k
wherein, L is the hole spacing of the nanoscale holes; k is a coefficient, and k is more than or equal to 1; the layer thickness is diffusion controlled.
Further, the inter-pore spacing between the nanoscale pores (2) is such that: l is less than or equal to 10.
Further, the inter-pore spacing between the nanoscale pores (2) is such that: l is less than or equal to 5.
Further, the inter-pore spacing between the nanoscale pores (2) is such that: l is less than or equal to 2.
Further, the inter-pore spacing between the nanoscale pores (2) is such that: l is less than or equal to.
Further, the array of nanoscale pores (2) is arranged on a side of the material body (1).
Further, the diffusion control layer has a thickness of:
Figure BDA0002020383270000021
wherein, the thickness of the diffusion control layer is shown; d is a diffusion coefficient; t is time.
Further, the thickness of the material body (1) is greater than or equal to 1 nm.
Further, the material body (1) is made of a metal material or a non-metal material.
Further, the metal material includes, but is not limited to, metallic lithium or metallic copper; the non-metallic material includes, but is not limited to, carbon, graphite, or graphene.
The invention also proposes an electrode comprising a substrate (3), said substrate (3) being provided on at least one of its two side faces with a nanoscale pore material (4) according to any one of claims 1 to 24.
Further, the base material (3) is made of copper foil, aluminum foil, steel foil or net-shaped copper foil.
The invention also proposes an energy storage device comprising an electronically insulating and ion-permeable membrane (5), said membrane (5) being provided on both sides with electrodes, respectively, said electrodes being as claimed in claim 25 or 26.
Further, the ion diaphragm is a battery diaphragm, and the electrodes arranged on two sides of the battery diaphragm are respectively a positive electrode and a negative electrode.
Further, the diaphragm is a capacitance diaphragm, and the electrodes arranged on both sides of the capacitance diaphragm are capacitance electrodes.
Further, the capacitance electrodes respectively arranged on the two sides of the diaphragm are made of the same capacitance electrode material; or the capacitance electrodes arranged on the two sides of the diaphragm are respectively made of different capacitance electrode materials.
Furthermore, one of the two electrodes positioned on two sides of the diaphragm is made of a battery anode material or an electrode cathode material, and the other electrode is made of a capacitance electrode material.
The invention has the beneficial effects that:
according to the nanoscale pore material, the nanoscale pores are formed in the side surface of the material body, when the nanoscale pore material is used on an electrode and energy storage equipment, electrolyte can be transmitted in the nanoscale pores, so that the specific surface area of the electrode is increased, the interior of the electrode can participate in charging and discharging, the specific power of the energy storage equipment is improved, and the utilization rate of the porous electrode is greatly improved; when the nanoscale pore is used in the field of biological medicine, the nanoscale pore can be used as a filtering pore, so that molecules with different sizes can be screened; of course, the nanoscale pores of the present invention have a variety of other fields of application, which will not be described in further detail.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
fig. 1 is a schematic structural diagram of an embodiment 1 of the nanoscale pore material of the present invention, specifically a schematic structural diagram of a 1 st nanoscale pore material;
FIG. 2 is a schematic view of a 2 nd structure of a nanoscale pore material;
FIG. 3 is a schematic diagram of a structure of type 3 of the nanoscale pore material;
FIG. 4 is a schematic diagram of a 4 th structure of a nanoscale pore material;
FIG. 5 is a schematic diagram of a 5 th structure of a nanoscale pore material;
FIG. 6 is a diagram of a 6 th structure of a nanoscale pore material;
FIG. 7 is a schematic diagram of a 7 th structure of a nanoscale pore material;
FIG. 8 is a schematic diagram of a structure 8 of a nanoscale pore material;
FIG. 9 is a schematic diagram of a 9 th structure of a nanoscale pore material;
FIG. 10 is a schematic structural diagram of an energy storage device of the present invention;
FIG. 11 is a schematic view of a first configuration of electrodes;
FIG. 12 is a schematic view of a second configuration of electrodes;
fig. 13 is a schematic view of a third structure of the electrode.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
Example 1
Fig. 1 is a schematic structural diagram of an example 1 of the nanoscale pore material of the present invention. The nanoscale hole material comprises a material body 1, wherein at least one side surface of the material body 1 is provided with a nanoscale hole 2.
Specifically, the nanoscale pores 2 of the present embodiment are blind pores provided on the side surfaces of the material body 1. Further, in two radial cross sections cut on the nanoscale hole 2 by any two planes perpendicular to the axis of the nanoscale hole 2, the area of the radial cross section closer to the bottom of the nanoscale hole 2 is less than or equal to the area of the radial cross section farther from the bottom of the nanoscale hole 2. As shown in fig. 1 to 5, the nano-scale holes 2 of various shapes can satisfy the condition that the area of the radial cross section closer to the bottom of the hole is smaller than or equal to the area of the radial cross section farther from the bottom of the hole, and the nano-scale holes 2 can also adopt other various structures, which will not be described again.
Of course, the nanoscale pores 2 may also be through-holes that extend through the body of material 1, as shown in fig. 6-9.
Further, two radial cross sections cut on the nanoscale hole 2 by any plane perpendicular to the axis of the nanoscale hole 2 in the present embodiment are similar figures, and the radial cross section may be a circle, an ellipse, a triangle, a square, a rectangle, a diamond, or a regular polygon, and the radial cross section of the present embodiment is a circle.
Further, the nanoscale wells 2 are arranged in an array. Of course, the nanoscale holes 2 can also be arranged in a gradient array, and the nanoscale holes 2 can be arranged in a gradient array with the aperture, the hole pitch or the hole shape as the reference, for example, the nanoscale holes 2 can be arranged in a gradient array with the aperture gradually changing from small to large, or in a gradient array with the hole pitch changing from small to large, or in a gradient array with the shape changing according to the arrangement rule, which is not described repeatedly.
Further, the pore diameter of the nanoscale pore 2 is greater than or equal to 1nm, and the pore diameter of the nanoscale pore 2 in this embodiment is greater than or equal to 2nm and less than or equal to 50nm, that is, the nanoscale pore 2 is a mesopore. Of course, the pore diameter of the nano-scale pores 2 can be set to be less than or equal to 1um, less than or equal to 100nm, and the like, which will not be described in detail.
Further, the pore spacing between the nanoscale pores 2 satisfies:
L≤k
wherein, L is the hole spacing of the nanoscale holes; k is a coefficient, and k is more than or equal to 1; the layer thickness is diffusion controlled.
Specifically, the pore spacing between the nanoscale pores 2 satisfies: l is less than or equal to 10. Preferably, the pore spacing between the nanoscale pores 2 is such that: l is less than or equal to 5. Preferably, the pore spacing between the nanoscale pores 2 is such that: l is less than or equal to 2. Preferably, the pore spacing between the nanoscale pores 2 is such that: l is less than or equal to. The pore spacing between the nanoscale pores 2 of the present example satisfies: l is less than or equal to, the influence of mass transfer or diffusion control can be eliminated, and when the porous electrode is used on an electrode and energy storage equipment, the specific power of the energy storage equipment can be improved, and the utilization rate of the porous electrode can be greatly improved. In particular, the array of nanoscale pores 2 of the present embodiment is disposed on a side of the body of material 1.
Further, the diffusion control layer thickness is:
Figure BDA0002020383270000051
wherein, the thickness of the diffusion control layer is shown; d is a diffusion coefficient; t is time.
The thickness of the material body 1 of the present embodiment is 1nm or more.
The material body 1 of the present embodiment is made of a metal material or a non-metal material. Specifically, the metal material includes metallic lithium or metallic copper, and the like, and the non-metal material includes carbon, graphite, graphene, or the like.
According to the nanoscale pore material, the nanoscale pores are formed in the side surface of the material body, when the nanoscale pore material is used on an electrode and energy storage equipment, electrolyte can be transmitted in the nanoscale pores, so that the specific surface area of the electrode is increased, the interior of the electrode can participate in charging and discharging, the specific power of the energy storage equipment is improved, and the utilization rate of the porous electrode is greatly improved; when the nanoscale pore is used in the field of biomedical science, the nanoscale pore can be used as a filter pore, so that molecules with different sizes can be screened.
Example 2
Fig. 10 is a schematic structural diagram of an embodiment of the energy storage device of the present invention. The energy storage device of the embodiment comprises an electronically insulated and ion-permeable membrane 5, and electrodes 6 and 7 are respectively arranged on two sides of the membrane 5. The electrode of the embodiment includes a substrate 3, and at least one of the two side surfaces of the substrate 3 is provided with a nanoscale porous material 4, and the nanoscale porous material 4 is as described in embodiment 1, which will not be described repeatedly. Specifically, the substrate 3 may be made of copper foil, aluminum foil, steel foil or mesh copper foil, and the substrate 3 of this embodiment is made of copper foil. .
Specifically, when the separator 5 is a battery separator, the electrodes disposed on both sides of the battery separator are a positive electrode and a negative electrode, respectively. When the diaphragm is a capacitance diaphragm, the electrodes arranged on the two sides of the capacitance diaphragm are capacitance electrodes, and when the capacitance electrodes arranged on the two sides of the diaphragm are made of the same capacitance electrode material, the capacitance is a symmetrical capacitance; when the capacitor electrodes arranged on the two sides of the diaphragm are respectively made of different capacitor electrode materials, the capacitor is an asymmetric capacitor. In addition, the energy storage device can also be a hybrid energy storage device, and at this time, one of the two electrodes positioned on the two sides of the diaphragm is made of a battery anode material or an electrode cathode material, and the other electrode is made of a capacitor electrode material.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims (31)

1. A nanoscale pore material, characterized by: comprises a material body (1), and nanoscale pores (2) are regularly distributed on at least one side surface of the material body (1).
2. The nanoscale pore material according to claim 1, characterized in that: the nanoscale hole (2) is a blind hole arranged on the side face of the material body (1).
3. The nanoscale pore material according to claim 2, characterized in that: in two radial cross sections of any two planes perpendicular to the axis of the nanoscale hole (2) and cut on the nanoscale hole (2), the area of the radial cross section closer to the hole bottom of the nanoscale hole (2) is less than or equal to the area of the radial cross section farther from the hole bottom of the nanoscale hole (2).
4. The nanoscale pore material according to claim 1, characterized in that: the nanoscale hole (2) is a through hole penetrating through the material body (1).
5. The nanoscale pore material according to any one of claims 1 to 4, characterized in that: two radial sections of any plane perpendicular to the axis of the nano-scale hole (2) and cut on the nano-scale hole (2) are similar in graph.
6. The nanoscale pore material according to claim 5, characterized in that: the radial section is circular, oval, triangular, square, rectangular, rhombic or regular polygonal.
7. The nanoscale pore material according to claim 1, characterized in that: the nanoscale holes (2) are arranged in an array.
8. The nanoscale pore material according to claim 1, characterized in that: the nanoscale holes (2) are arranged in a gradient array.
9. The nanoscale pore material according to claim 8, characterized in that: the nanoscale holes (2) are arranged in a gradient array by taking the aperture, the hole spacing or the hole shape as a reference.
10. The nanoscale pore material according to claim 1, characterized in that: the pore diameter of the nanoscale pores (2) is greater than or equal to 1 nm.
11. The nanoscale pore material according to claim 10, characterized in that: the aperture of the nanoscale hole (2) is less than or equal to 1 um.
12. The nanoscale pore material according to claim 11, characterized in that: the pore diameter of the nanoscale pores (2) is less than or equal to 100 nm.
13. The nanoscale pore material according to claim 12, characterized in that: the pore diameter of the nanoscale pores (2) is less than or equal to 50 nm.
14. The nanoscale pore material according to claim 13, characterized in that: the pore diameter of the nanoscale pores (2) is greater than or equal to 2 nm.
15. The nanoscale pore material according to claim 1, characterized in that: the pore spacing between the nanoscale pores (2) satisfies:
L≤k
wherein, L is the hole spacing of the nanoscale holes; k is a coefficient, and k is more than or equal to 1; the layer thickness is diffusion controlled.
16. The nanoscale pore material according to claim 15, characterized in that: the pore spacing between the nanoscale pores (2) satisfies: l is less than or equal to 10.
17. The reduced nanoscale pore material of claim 16, wherein: the pore spacing between the nanoscale pores (2) satisfies: l is less than or equal to 5.
18. The nanoscale pore material of claim 17, wherein: the pore spacing between the nanoscale pores (2) satisfies: l is less than or equal to 2.
19. The nanoscale pore material of claim 18, wherein: the pore spacing between the nanoscale pores (2) satisfies: l is less than or equal to.
20. The nanoscale pore material of claim 19, wherein: the array of nanoscale pores (2) is arranged on a side face of the material body (1).
21. The nanoscale pore material according to any one of claims 15-20, characterized in that: the thickness of the diffusion control layer is as follows:
Figure FDA0002020383260000021
wherein, the thickness of the diffusion control layer is shown; d is a diffusion coefficient; t is time.
22. The nanoscale pore material of claim 1, wherein: the thickness of the material body (1) is more than or equal to 1 nm.
23. The nanoscale pore material according to claim 1, characterized in that: the material body (1) is made of a metal material or a non-metal material.
24. The nanoscale pore material according to claim 23, characterized in that: the metal material includes, but is not limited to, metallic lithium or metallic copper; the non-metallic material includes, but is not limited to, carbon, graphite, or graphene.
25. An electrode, characterized by: comprising a substrate (3), said substrate (3) being provided on at least one of its two side surfaces with a nanoscale pore material (4) as claimed in any of claims 1 to 24.
26. The electrode of claim 26, wherein: the base material (3) is made of copper foil, aluminum foil, steel foil or net-shaped copper foil.
27. An energy storage device, characterized by: -a membrane (5) which is electronically insulating and ion permeable, -electrodes being provided on both sides of the membrane (5), respectively, the electrodes being as claimed in claim 25 or 26.
28. The energy storage device of claim 27, wherein: the ion diaphragm is a battery diaphragm, and the electrodes arranged on the two sides of the battery diaphragm are respectively a positive electrode and a negative electrode.
29. The energy storage device of claim 27, wherein: the diaphragm is a capacitance diaphragm, and the electrodes arranged on two sides of the capacitance diaphragm are capacitance electrodes.
30. The energy storage device of claim 29, wherein: the capacitance electrodes respectively arranged on the two sides of the diaphragm are made of the same capacitance electrode material; or the capacitance electrodes arranged on the two sides of the diaphragm are respectively made of different capacitance electrode materials.
31. The energy storage device of claim 27, wherein: and one of the two electrodes positioned at two sides of the diaphragm is made of a battery anode material or an electrode cathode material, and the other electrode is made of a capacitance electrode material.
CN201910277053.0A 2019-04-08 2019-04-08 Nanoscale hole material, electrode and energy storage equipment Pending CN111799431A (en)

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Application Number Priority Date Filing Date Title
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