CN113540469B - Current collector, lithium-sulfur battery positive plate containing current collector and lithium-sulfur battery - Google Patents
Current collector, lithium-sulfur battery positive plate containing current collector and lithium-sulfur battery Download PDFInfo
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- CN113540469B CN113540469B CN202010316079.4A CN202010316079A CN113540469B CN 113540469 B CN113540469 B CN 113540469B CN 202010316079 A CN202010316079 A CN 202010316079A CN 113540469 B CN113540469 B CN 113540469B
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 34
- 239000011593 sulfur Substances 0.000 claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
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- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- 239000011149 active material Substances 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002482 conductive additive Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000002002 slurry Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000005077 polysulfide Substances 0.000 abstract description 4
- 229920001021 polysulfide Polymers 0.000 abstract description 4
- 150000008117 polysulfides Polymers 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 239000011888 foil Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a current collector which comprises an aluminum wire framework and a carbon layer coated on the aluminum wire framework, wherein the thickness of the carbon layer is 2-50 nm; the carbon layer is formed by heat treatment of polyacrylonitrile at 250-450 ℃ in an inert atmosphere. The current collector contains the carbon layer, so that the adhesive force between the current collector and the coated slurry is enhanced, the coating of a high-load anode material is facilitated, the problem that powder is easy to fall off when the high-load anode is coated is solved, the contact resistance is reduced, and the rate capability of the anode is facilitated to be enhanced; the carbon layer is formed by heat treatment of polyacrylonitrile at 250-450 ℃, CN bonds are still reserved in the carbon layer, the carbon layer has an adsorption effect on polysulfide generated in the discharge process of the sulfur anode, and the cycle characteristic of the anode is effectively improved. The invention also provides a preparation method of the current collector. The invention also provides a lithium-sulfur battery positive plate. The invention also provides a lithium-sulfur battery.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a current collector, a lithium-sulfur battery positive plate containing the current collector and a lithium-sulfur battery.
Background
With the vigorous development of the national new energy industry, people have higher and higher requirements on endurance mileage. The energy density of the conventional lithium ion battery is close to the limit due to the limit of the capacity of the conventional lithium ion battery, so that the attention of the lithium ion battery to the next generation energy storage device with higher energy density is high. Lithium-sulfur batteries have been developed because of their ultra-high theoretical energy density (2600 Wh kg) -1 ) And the advantages of low cost of raw materials, good environmental adaptability and the like attract the wide attention of researchers. However, lithium sulfur batteries also face a number of challenges: sulfur has poor conductivity, and polysulfide, a reaction intermediate, is easily dissolved in an electrolyte and generates a shuttle effect, and there have been many methods for improving these problems. In addition, high sulfur loading in commercial oriented applicationsThe sulfur positive electrode has a more practical significance, and generally, due to the limitations of the current commercial aluminum foil current collectors, such as the problem that the electron transmission rate is reduced when the current aluminum foil current collector is in a high-load state and the problem that the current aluminum foil current collector is easy to remove powder when the current aluminum foil current collector is thick, the rate performance and the capacity exertion of the sulfur positive electrode are reduced along with the improvement of the sulfur load. However, the Al foam current collectors that have appeared on the market also have problems such as poor contact with the slurry coating.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a current collector, a lithium-sulfur battery positive plate containing the current collector and a lithium-sulfur battery.
In order to achieve the purpose, the invention adopts the technical scheme that: a current collector comprises an aluminum wire framework and a carbon layer coated on the aluminum wire framework, wherein the thickness of the carbon layer is 2-50 nm; the carbon layer is formed by heat treatment of polyacrylonitrile at 250-450 ℃ in an inert atmosphere.
The current collector adopts the aluminum wire framework coated with the carbon layer, is of a three-dimensional net structure, can enhance the adhesive force between the current collector and the coated slurry by the carbon layer, is particularly suitable for the anode current collector of a lithium-sulfur battery, is beneficial to coating of a high-load anode material, relieves the problem of easy powder falling during coating of the high-load anode, reduces the contact resistance, and is beneficial to enhancing the multiplying power performance of the anode. The carbon layer is formed by heat treatment of polyacrylonitrile at 250-450 ℃, CN bonds are still reserved in the carbon layer, the carbon layer has an adsorption effect on polysulfide generated in the discharge process of the sulfur anode, and the cycle characteristic of the anode is effectively improved. The carbon layer formed by the heat treatment of polyacrylonitrile at an excessively high temperature retains less or no CN bonds, and thus the function of CN bonds is hardly exerted. The inventor researches and discovers that when the thickness of the carbon layer is 2-50 nm, the carbon layer is not too thick and is easy to fall off, and when the thickness is not too low, the cycle performance and the rate performance of the battery are not remarkably improved.
The polyacrylonitrile can select the polyacrylonitrile with proper viscosity according to the specific adhesion condition.
In a more preferred embodiment of the current collector of the present invention, the carbon layer is formed by heat-treating polyacrylonitrile at 300 to 450 ℃ in an inert atmosphere.
In a preferred embodiment of the current collector of the present invention, the carbon layer has a thickness of 2 to 5nm. When the thickness of the carbon layer is 2-5 nm, the cycle performance and the rate performance of the battery can be effectively improved, and the falling rate is lowest.
In a preferred embodiment of the current collector of the present invention, the pore diameter of the aluminum wire framework is 0.3 to 0.8mm.
In a preferred embodiment of the current collector of the present invention, the porosity of the aluminum wire skeleton is 92 to 97%. Under the pore diameter and porosity, the aluminum wire framework in unit volume can load more sulfur-containing active substances.
The invention also aims to provide a preparation method of the current collector, which comprises the following steps:
(1) Coating polyacrylonitrile on an aluminum wire framework, drying, placing in an inert atmosphere, and performing heat treatment at 250-450 ℃ for 10-60 min;
(2) And (4) repeating the step (1) to reach the thickness of the required carbon layer, and obtaining the current collector.
The carbon layer can be tightly attached to the aluminum wire framework by adopting the preparation method, and the method is simple, has strong operability and is suitable for large-scale industrial application.
The invention also aims to provide a positive plate of the lithium-sulfur battery, which comprises the current collector and a sulfur-containing active material attached to the current collector. The sulfur-containing active substance is a mixture containing sulfur, a carbon material, a conductive additive and a binder, and is attached to the current collector to form the lithium-sulfur battery positive plate, which is particularly suitable for loading high-load sulfur.
As a preferred embodiment of the positive electrode plate of the lithium-sulfur battery, the sulfur-containing active material comprises the following components in percentage by weight: 50-80% of sulfur, 10-20% of carbon material, 5-10% of conductive additive and 7-15% of adhesive. The sulfur may be sublimed sulfur, the carbon material may be a porous carbon material, the conductive additive may be carbon nanotubes and conductive carbon black, and the binder may be PVDF and polyacrylonitrile.
In a preferred embodiment of the positive electrode sheet for a lithium-sulfur battery according to the present invention, the sulfur is contained in the sulfur-containing active material in an amount of 60 to 80% by weight. When the sulfur carrying capacity is adopted, the advantage of high energy density of the lithium-sulfur battery can be fully exerted.
As a preferable embodiment of the positive plate of the lithium-sulfur battery, the content of the sulfur on the current collector is 3-6 mg/cm 2 . By adopting the current collector disclosed by the invention, the sulfur carrying capacity has better rate capability and higher capacity.
The invention also aims to provide a lithium-sulfur battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is the positive plate of the lithium-sulfur battery.
The invention has the beneficial effects that: the invention provides a current collector, which adopts an aluminum wire framework coated with a carbon layer, is of a three-dimensional net structure, and the carbon layer can enhance the bonding force between the current collector and coated slurry, thus being beneficial to coating of a high-load anode material, relieving the problem of easy powder falling during coating of the high-load anode, reducing contact resistance and being beneficial to enhancing the rate capability of the anode; the carbon layer is formed by heat treatment of polyacrylonitrile at 250-450 ℃, CN bonds are still reserved in the carbon layer, the carbon layer has an adsorption effect on polysulfide generated in the discharge process of the sulfur anode, and the cycle characteristic of the anode is effectively improved. The invention also provides a preparation method of the current collector, the preparation method can enable the carbon layer to be tightly attached to the aluminum wire framework, and the method is simple, strong in operability and suitable for large-scale industrial application. The invention also provides a lithium-sulfur battery positive plate which has high rate capability and cycle capability. The invention also provides a lithium-sulfur battery.
Drawings
FIG. 1 is a graph of rate performance of lithium batteries of example 1, example 3, comparative example 1, and comparative example 3;
FIG. 2 is a graph showing cycle performance of lithium batteries according to examples 1, 1 and 2;
FIG. 3 is a graph of the cycle performance of the positive electrodes of examples 1, 4, 5;
fig. 4 is an infrared spectrum of the current collector and polyacrylonitrile described in example 1, example 3 and comparative example 3.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
In the examples of the present invention and the comparative examples, the method for preparing the porous carbon material includes the steps of:
(1) Adding 50g of pretreated ion exchange resin into 200ml of 0.2mol/L cobalt chloride aqueous solution, stirring for 2 hours, putting into 80 ℃ water bath, stirring, evaporating to dryness, drying by blowing at 80 ℃ for 12 hours, and crushing to obtain resin for adsorbing cobalt ions;
(2) Dissolving 100g of potassium hydroxide in 400ml of absolute ethanol to form a potassium hydroxide/ethanol solution, dissolving 100g of calcium hydroxide in 400ml of water to form a calcium hydroxide/water solution, adding the product obtained in the step 1 into the potassium hydroxide/ethanol and calcium hydroxide/water solution, putting the mixture into an oil bath at 80 ℃, stirring and evaporating the mixture until the mixture is pasty, drying the mixture at 80 ℃, and then crushing the mixture again;
(3) Heating the product obtained in the step (2) to 800 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the heat for 2 hours, and naturally cooling to room temperature;
(4) And (4) soaking the product obtained in the step (3) in 1mol/L hydrochloric acid solution for 36 hours, filtering, drying at 60 ℃ for 36 hours, and continuing to dry at 150 ℃ for 8 hours to obtain the porous carbon material.
In the examples and comparative examples, the pore diameter of the aluminum wire framework is 0.5mm, the thickness is 1mm, and the porosity is 95%; polyacrylonitrile was purchased from Sigma-Aldrich and had a molecular weight of 150000; the conductive additive is super carbon black which is purchased from Shenzhenjac Jingzhida science and technology Limited.
Example 1
The preparation method of the current collector in this embodiment includes the following steps: soaking an aluminum wire framework in 5wt% polyacrylonitrile solution for 1h, taking out, standing in the air, naturally drying, then placing in a tube furnace, and carrying out heat treatment in inert gas at 300 ℃ for 10min to obtain the current collector.
The positive plate of the lithium-sulfur battery in this embodiment includes the current collector in this embodiment and a sulfur-containing active material attached to the current collector, where the sulfur-containing active material includes the following components in percentage by weight: 60% of sublimed sulfur, 25% of porous carbon material, 5% of super carbon black and 10% of polyacrylonitrile.
The preparation method of the lithium battery comprises the following steps: uniformly mixing all components of the sulfur-containing active substance to prepare slurry, and coating the slurry on a current collector, wherein the sulfur loading capacity is 3mg/cm 2 And drying, compacting, cutting, assembling into a CR2032 battery in a glove box according to a conventional method, and testing.
Example 2
The method for preparing the current collector in this example is different from that in example 1 only in the temperature of the heat treatment, which is 400 ℃.
Except for adopting the current collector in the embodiment, the positive plate of the lithium-sulfur battery is the same as that in embodiment 1. The lithium battery was prepared in the same manner as in example 1.
Example 3
The method for preparing the current collector in this example is different from that in example 1 only in the temperature of the heat treatment, which is 450 ℃.
The lithium-sulfur battery positive plate described in this example is the same as that described in example 1 except that the current collector described in this example is used. The lithium battery was prepared in the same manner as in example 1.
Example 4
The preparation method of the current collector in this embodiment is the same as that in embodiment 1; the difference between the positive plate of the lithium-sulfur battery and the lithium battery in the embodiment 1 is only the difference of the sulfur loading capacity, and the sulfur loading capacity in the embodiment is 4mg/cm 2 。
Example 5
The preparation method of the current collector in this embodiment is the same as that in embodiment 1; the lithium-sulfur battery positive electrode sheet and lithium battery described in this example are different from those of example 1The only difference is the sulfur loading, which is 6mg/cm in this example 2 。
Comparative example 1
The current collector of this comparative example is an aluminum wire skeleton without a carbon layer. The same procedure as in example 1 was repeated except that the current collector of the present comparative example was used in the positive electrode sheet of the lithium-sulfur battery of the present comparative example. The lithium battery was prepared in the same manner as in example 1.
Comparative example 2
The current collector of this comparative example was a planar aluminum foil. The lithium-sulfur battery positive plate of the comparative example is the same as example 1 except that the current collector of the comparative example is adopted. The lithium battery was prepared in the same manner as in example 1.
Comparative example 3
The method of manufacturing the current collector described in this comparative example is different from example 1 only in the temperature of the heat treatment, which is 500 ℃. The same procedure as in example 1 was repeated except that the current collector of the present comparative example was used in the positive electrode sheet of the lithium-sulfur battery of the present comparative example. The lithium battery was prepared in the same manner as in example 1. The current collector prepared in this comparative example was easily crushed.
Example 6
FIG. 1 is a graph of rate performance for lithium batteries described in examples 1, 3, comparative examples 1 and 3;
fig. 2 is a graph showing cycle performance of lithium batteries according to example 1, comparative example 1 and comparative example 2.
As can be seen from fig. 1 and 2, the positive electrode rate of the current collectors formed according to examples 1 and 3 is significantly better than that of the current collector without the carbon layer and the current collector after heat treatment at 500 ℃. The current collector of example 1 gave significantly better cycle performance than comparative example 1 of the current collector without the carbon layer and comparative example 2 of the planar aluminum foil.
Fig. 3 shows cycle performance of the positive electrodes of examples 1, 4 and 5. 6mg/cm 2 The lower 0.5C still gives off higher capacity, indicating that the current collectors of the invention may exhibit advantages at high sulfur loadings.
Fig. 4 is an infrared spectrum of the current collector and polyacrylonitrile described in example 1, example 3 and comparative example 3, and it can be seen from fig. 4 that C = N is formed on the current collector after heat treatment at 300 ℃, the bond is still formed on the current collector after heat treatment at 450 ℃, carbonization is not completed, and C = N is less on the current collector after heat treatment at 500 ℃.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The current collector is characterized by being applied to a positive current collector of a lithium-sulfur battery, and comprising an aluminum wire framework and a carbon layer coated on the aluminum wire framework, wherein the thickness of the carbon layer is 2-50 nm; the carbon layer is formed by heat treatment of polyacrylonitrile at 250-450 ℃ in inert atmosphere, CN bonds are reserved in the carbon layer, and the porosity of the aluminum wire framework is 92-97%;
and the thickness of the carbon layer is 2-5 nm.
2. The current collector of claim 1, wherein the aluminum wire framework has a pore size of 0.3 to 0.8mm.
3. The method for manufacturing a current collector according to any one of claims 1 to 2, comprising the steps of:
(1) Coating polyacrylonitrile on the aluminum wire framework, drying, placing in an inert atmosphere, and performing heat treatment at 250-450 ℃ for 10-60 min;
(2) And (4) repeating the step (1) to reach the thickness of the required carbon layer, and obtaining the current collector.
4. A positive electrode sheet for a lithium-sulfur battery, comprising the current collector of any one of claims 1 to 2 and a sulfur-containing active material attached to the current collector.
5. The positive plate of the lithium-sulfur battery as claimed in claim 4, wherein the sulfur-containing active material comprises the following components in percentage by weight: 50-80% of sulfur, 10-20% of carbon material, 5-10% of conductive additive and 7-15% of adhesive.
6. The positive electrode sheet for a lithium-sulfur battery as claimed in claim 5, wherein the sulfur is contained in the active material in an amount of 60 to 80% by weight.
7. The positive plate of the lithium-sulfur battery as claimed in claim 5, wherein the content of the sulfur on the current collector is 3 to 6mg/cm 2 。
8. A lithium-sulfur battery, comprising a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte, wherein the positive electrode sheet is the positive electrode sheet of the lithium-sulfur battery according to any one of claims 4 to 7.
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| CN113540469A (en) | 2021-10-22 |
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