CN111653757B - Flexible self-supporting tellurium nanotube composite electrode, preparation method thereof and flexible battery - Google Patents
Flexible self-supporting tellurium nanotube composite electrode, preparation method thereof and flexible battery Download PDFInfo
- Publication number
- CN111653757B CN111653757B CN202010340734.XA CN202010340734A CN111653757B CN 111653757 B CN111653757 B CN 111653757B CN 202010340734 A CN202010340734 A CN 202010340734A CN 111653757 B CN111653757 B CN 111653757B
- Authority
- CN
- China
- Prior art keywords
- tellurium
- flexible
- supporting
- composite electrode
- tellurium nanotube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002071 nanotube Substances 0.000 title claims abstract description 153
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 142
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims description 16
- 239000006185 dispersion Substances 0.000 claims description 63
- 239000007788 liquid Substances 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000011159 matrix material Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 16
- 239000012498 ultrapure water Substances 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 238000003828 vacuum filtration Methods 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 229920001046 Nanocellulose Polymers 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 239000013543 active substance Substances 0.000 abstract description 9
- 239000011230 binding agent Substances 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 239000006258 conductive agent Substances 0.000 abstract description 8
- 229920002678 cellulose Polymers 0.000 description 35
- 239000001913 cellulose Substances 0.000 description 35
- 238000001914 filtration Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000011149 active material Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000004729 solvothermal method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000007605 air drying Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a flexible self-supporting tellurium nanotube composite electrode which comprises a flexible substrate layer and an active substance layer arranged on the flexible substrate layer, wherein the active substance layer comprises tellurium nanotubes. The flexible self-supporting tellurium nanotube composite electrode does not need an additional current collector, a conductive agent and a binder, has the characteristics of high active substance content, light weight, good flexibility and the like, and has higher charge and discharge capacity and better cycle stability when being used as a lithium ion battery electrode. The invention also provides the flexible self-supporting tellurium nanotube composite electrode and a flexible battery.
Description
Technical Field
The invention relates to the field of electrode material preparation, in particular to a flexible self-supporting tellurium nanotube composite electrode, a preparation method of the flexible self-supporting tellurium nanotube composite electrode, and a flexible battery comprising the flexible self-supporting tellurium nanotube composite electrode.
Background
With the development of modern science and technology, electronic products are gradually developing towards the directions of lightness, thinness, wearability and folding, and concept products of flexible devices are produced at the same time. The lithium ion battery has the advantages of light weight, high specific power, high energy density, excellent rate performance and the like, and has unique advantages when being used as an energy storage device of flexible electrons. However, when the conventional lithium ion battery electrode is bent and folded, the electrode material and the current collector are easily separated, the electrochemical performance is affected, even short circuit is caused, and a serious safety problem occurs. At present, the electrode of the flexible battery is obtained by mainly replacing metal current collectors such as aluminum foil and copper foil with a flexible matrix and loading a powder active material on the flexible matrix.
The cellulose is a natural biological material with the largest amount in nature, and the nano-cellulose obtained after degradation has high specific surface area, excellent mechanical property, good biocompatibility and degradability, and is commonly used as a flexible matrix and a binder in a flexible electrode of a lithium ion battery. For example, patent publication No. CN107611342A discloses a flexible lithium ion battery electrode sheet using a cushion layer, wherein the cushion layer is formed by suction filtration of a suspension of nanocellulose, and a base material disposed on the cushion layer is formed by mixing and suction filtration of nanocellulose as a matrix, a conventional powder active material such as lithium cobaltate or graphite particles, a conductive agent such as conductive carbon black, and polyvinylidene fluoride as a binder. The flexible electrode does not need to use a metal current collector, realizes self-supporting and has better mechanical property and flexibility. The patent publication No. CN105140523A discloses a method for preparing a flexible thin film electrode for a lithium ion battery, which takes lithium cobaltate, lithium iron phosphate, etc. or graphite, carbon microspheres, etc. as positive and negative electrode active materials, takes cellulose as a binder, takes carbon nanotubes, graphene, acetylene black, etc. as a conductive agent, adds a proper amount of dispersant and plasticizer, and synthesizes the flexible thin film electrode with good mechanical properties and good cycling stability through ultrasonic dispersion, filter pressing and drying.
Although the above patents improve the mechanical properties of the electrode to a certain extent, the conventional powder active material itself is rigid, which greatly limits the further improvement of the flexibility of the electrode, and the whole energy density of the flexible device is also reduced because a large proportion of inactive substances such as flexible substrates, binders, conductive agents and the like need to be added in the preparation process. As a key energy storage component of a flexible device, an ideal flexible battery must combine excellent flexibility and electrochemical performance, however, the two tend to mutually engage, and therefore, designing and developing an electrode having high flexibility and high performance becomes a major challenge for the flexible battery.
Disclosure of Invention
In view of this, the invention provides a flexible self-supporting tellurium nanotube composite electrode and a preparation method thereof, the flexible self-supporting tellurium nanotube composite electrode comprises an active material-tellurium nanotubes with a flexible self-supporting function, the flexibility of the electrode is greatly improved because the active material is flexible, and in the preparation process, inactive materials such as a binder and a conductive agent are not required to be added, so that the overall energy density of a flexible device is improved. The invention also provides a flexible battery comprising the flexible self-supporting tellurium nanotube composite electrode, and the flexibility and the electrochemical performance of the flexibility of the flexible battery are further improved by the flexible self-supporting tellurium nanotube composite electrode.
In a first aspect, the invention provides a flexible self-supporting tellurium nanotube composite electrode, which comprises a flexible substrate layer and an active material layer arranged on the flexible substrate layer, wherein the active material layer comprises tellurium nanotubes.
Preferably, the tellurium nanotubes have a diameter of 30 to 100nm, and specifically may have a diameter of 30nm, 50nm, 70nm, 80nm or 100nm. The tellurium nanotubes account for 80-95% of the total mass of the flexible self-supporting tellurium nanotube composite electrode, and specifically may be 80%, 85%, 90% or 95%.
Preferably, the flexible matrix layer comprises nanocellulose, and the diameter of the nanocellulose is 5-20 nm, and specifically may be 5nm, 10nm, 15nm or 20nm. The length of the nanocellulose is 400 to 500. Mu.m, and may be, for example, 400. Mu.m, 450. Mu.m, or 500. Mu.m.
Preferably, the nanocellulose accounts for 5-20% of the total mass of the flexible self-supporting tellurium nanotube composite electrode, and may be 5%, 10%, 15% or 20%, for example.
Preferably, the flexible substrate layer is composed of nanocellulose, and the active material layer is composed of tellurium nanotubes.
The flexible self-supporting tellurium nanotube composite electrode comprises a flexible substrate layer and an active substance layer arranged on the flexible substrate layer, and the tellurium nanotubes are tightly loaded on the flexible substrate layer to form the self-supporting flexible composite electrode without additional current collectors, conductive agents and binders. The composite electrode has good flexibility, and has higher charge and discharge capacity and better cycle stability when used as an electrode of a lithium ion battery. Compared with the traditional battery material, the tellurium nanotube is adopted as the active substance, so that on one hand, the intrinsic conductivity is excellent, the theoretical specific capacity and the volume energy density are high when the tellurium nanotube is used as the electrode material of the lithium ion battery, on the other hand, the tellurium nanotube has the characteristics of large specific surface area, high flexibility, easiness in assembling and film forming and the like of a low-dimensional nano material, and the content of a flexible matrix can be reduced without additionally adding a conductive agent and a binder, so that the content of the active substance is increased, and the overall weight of the electrode is reduced. The composite electrode with a self-supporting structure can be formed only by adopting a small amount of flexible base materials with rich sources and low cost as the flexible matrix of the electrode and avoiding using a metal current collector, and meanwhile, the mechanical property of the electrode is greatly improved.
In a second aspect, the invention also provides a preparation method of the flexible self-supporting tellurium nanotube composite electrode, which comprises the following steps in parts by weight:
preparing a tellurium nanotube dispersion liquid: adding the tellurium nanotubes into absolute ethyl alcohol, and performing ultrasonic dispersion to obtain a tellurium nanotube dispersion liquid;
preparing a flexible matrix dispersion liquid: adding the flexible matrix into absolute ethyl alcohol, and uniformly stirring to obtain flexible matrix dispersion liquid;
preparing a flexible self-supporting tellurium nanotube composite electrode: and (3) performing suction filtration on the flexible matrix dispersion liquid by adopting a vacuum filtration method, adding the tellurium nanotube dispersion liquid, continuously performing suction filtration to obtain a composite film with a lower layer as a flexible matrix and an upper layer as a tellurium nanotube, drying, and cutting to obtain the flexible self-supporting tellurium nanotube composite electrode.
In one embodiment of the present invention, in the step of preparing the tellurium nanotube dispersion, the method for preparing the tellurium nanotubes comprises:
addition of Na to ultrapure water 2 TeO 3 Stirring polyvinylpyrrolidone to obtain transparent solution, adding acetone, mixing, adding ammonia water and hydrazine hydrate, transferring the obtained mixed solution into a reaction kettle for hydrothermal reaction, naturally cooling the reactant to room temperature, pouring outAnd (4) washing, centrifuging and drying the obtained precipitate to obtain the tellurium nanotubes. Na (Na) 2 TeO 3 As a Te source, polyvinylpyrrolidone (PVP) is used as a surfactant, and the tellurium nanotubes prepared by a macromolecule assisted solvothermal method have uniform appearance and size.
Preferably, in the step of preparing the tellurium nanotube dispersion, the Na is present in parts by weight 2 TeO 3 The ratio of the consumption of the polyvinylpyrrolidone, the ultrapure water, the acetone, the ammonia water and the hydrazine hydrate is (1).
Preferably, the reaction kettle is a reaction kettle with a polytetrafluoroethylene inner container, the hydrothermal reaction temperature is 150-200 ℃, and the reaction time is 3-10 h.
In another embodiment of the present invention, the tellurium nanotubes, tellurium nanotube dispersions, flexible matrix dispersions, etc. can also be prepared by other methods or purchased.
Preferably, in the step of preparing the tellurium nanotube dispersion liquid, the concentration of the tellurium nanotube dispersion liquid is 0.05-2 mg/ml, and the ultrasonic time is 0.5-1 h.
Preferably, in the step of preparing the flexible matrix dispersion, the concentration of the flexible matrix dispersion is 0.01 to 1mg/ml.
Preferably, in the step of preparing the flexible matrix dispersion liquid, the stirring is magnetic stirring, the rotating speed is 500-1000 r/min, and the stirring time is 0.5-1 h.
Preferably, in the step of preparing the flexible self-supporting tellurium nanotube composite electrode, the flexible matrix is nano-cellulose, wherein the tellurium nanotubes account for 80-95% of the total mass of the flexible self-supporting tellurium nanotube composite electrode, and the nano-cellulose accounts for 5-20% of the total mass of the flexible self-supporting tellurium nanotube composite electrode.
The preparation method of the flexible self-supporting tellurium nanotube composite electrode in the second aspect of the invention has the advantages of simple steps and low cost, and can be used for large-scale industrial production. The flexible self-supporting tellurium nanotube composite electrode prepared by the method has the characteristics of high active substance content, light weight, good flexibility, high charge-discharge specific capacity and the like, can effectively overcome the defects of insufficient capacity, low energy density, insufficient flexibility and the like of the conventional flexible battery, and has great advantages in the application of flexible electrodes such as lithium ion batteries and the like.
In a third aspect, the invention also provides a flexible battery comprising a flexible self-supporting tellurium nanotube composite electrode according to the first aspect of the invention.
The flexible self-supporting tellurium nanotube composite electrode has high theoretical specific capacity and volume energy density when being applied to a flexible battery, has the characteristics of large specific surface area, high flexibility, easy assembly and film forming and the like of a low-dimensional nano material, does not need to additionally add a conductive agent and a binder, and can reduce the content of a flexible matrix, thereby improving the content of active substances and lightening the overall weight of the electrode. The flexible battery has the characteristics of high active substance content, light weight, good flexibility, high charge-discharge specific capacity and the like, and can effectively overcome the defects of insufficient capacity, low energy density, insufficient flexibility and the like of the conventional flexible battery.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
In order to more clearly illustrate the contents of the present invention, a detailed description thereof will be given below with reference to the accompanying drawings and specific embodiments.
FIG. 1 is an SEM photograph of Te nanotubes obtained in example 1 of the present invention;
FIG. 2 is a TEM image of Te nanotubes obtained in example 1 of the present invention;
FIG. 3 is an XRD pattern of the tellurium nanotubes obtained in example 1 of the present invention;
FIG. 4 is a photograph of the flexible self-supporting Te nanotube composite electrode obtained in example 1 of the present invention before and after bending;
FIG. 5 is an SEM image of the flexible self-supporting Te nanotube composite electrode obtained in example 1 of the present invention;
FIG. 6 is a SEM image of a cross-section of the flexible self-supporting Te nanotube composite electrode obtained in example 1 of the present invention;
FIG. 7 is a graph of the cycle performance of the flexible self-supporting Te nanotube composite electrode obtained in example 1 of the present invention;
FIG. 8 is the photos of the flexible self-supporting Te nanotube composite electrode obtained in example 2 of the present invention before and after bending;
FIG. 9 is an SEM image of the flexible self-supporting Te nanotube composite electrode obtained in example 2 of the present invention;
fig. 10 is a cycle performance graph of the flexible self-supporting tellurium nanotube composite electrode obtained in example 2 of the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood that various modifications and adaptations of the present invention may occur to one skilled in the art without departing from the spirit of the present invention and are intended to be included within the scope of the present invention.
Example 1
A preparation method of the flexible self-supporting tellurium nanotube composite electrode comprises the following four steps of S1, S2, S3 and S4:
s1, preparing a tellurium nanotube by a polymer-assisted solvothermal method:
0.25g of Na was taken 2 TeO 3 And 3g PVP dissolved in 150ml ultrapure water and stirred for 10min, then 50ml acetone is added and stirring is continued for 10min, finally 15ml ammonia water and 7.5ml hydrazine hydrate are added and stirring is continued for 20min. Transferring the obtained mixed solution into five parts, adding the five parts into a reaction kettle with five polytetrafluoroethylene inner containers with the capacity of 50ml, and transferring the reaction kettle into an oven with the temperature of 180 ℃ for reaction for 4 hours. And naturally cooling the reacted solution, pouring out supernatant, washing the obtained precipitate by adopting ultrapure water, centrifuging, repeating the washing and centrifuging for three times, collecting the precipitate, drying the precipitate in a forced air drying oven at 80 ℃ for 8 hours, and detecting the phase and the morphology of the obtained product. Fig. 1 and fig. 2 are SEM and TEM images of the tellurium nanotubes, respectively, and it can be seen that tellurium nanotubes having uniform morphology and uniform size were successfully synthesized, and the average diameter of the tellurium nanotubes was 80nm. FIG. 3 is an XRD pattern of tellurium nanotubes, wherein the lower spectrum corresponds to standard sample Te, which may beSo that the product is very pure and no other impurity substances exist.
S2, preparing a tellurium nanotube dispersion liquid:
and adding 2mg of tellurium nanotubes into 20ml of absolute ethyl alcohol, and performing ultrasonic dispersion for 0.5h to obtain a tellurium nanotube dispersion liquid.
S3, preparing a nano-cellulose dispersion liquid:
4g of nano-cellulose with solid content of 5 percent is added into 20ml of absolute ethyl alcohol solvent and stirred for 0.5h at the rotating speed of 500r/min to obtain nano-cellulose dispersion liquid.
S4, preparing a flexible self-supporting tellurium nanotube composite electrode:
and uniformly adding the nano-cellulose dispersion liquid into a vacuum filtration device, and then uniformly adding the tellurium nanotube dispersion liquid into the vacuum filtration device for continuous filtration. And after the suction filtration is finished, drying the film taken off from the filter paper in a forced air drying oven at the temperature of 80 ℃ for 12 hours to finally obtain the composite electrode with the lower layer of the nano-cellulose and the upper layer of the tellurium nanotubes.
And detecting the morphology and the electrochemical performance of the obtained composite electrode. Fig. 4 is photographs before and after bending of the flexible self-supporting tellurium nanotube composite electrode obtained in example 1, and it can be seen that the obtained composite electrode has a self-supporting structure, a relatively smooth surface, good flexibility, and no damage to the integrity of the electrode in a bent state. Fig. 5 is an SEM image of the flexible self-supporting tellurium nanotube composite electrode obtained in example 1 of the present invention, in which the tellurium nanotubes are tightly interlaced to form an electrode active material layer. Fig. 6 is an SEM image of the cross section of the flexible self-supporting tellurium nanotube composite electrode obtained in example 1 of the present invention, which shows that the entire electrode is composed of two layers, the upper layer is an active material layer formed by interweaving tellurium nanotubes, and the bottom layer is a flexible substrate layer composed of nanocellulose, which provides support for the entire electrode and further increases the flexibility of the electrode. FIG. 7 is a cycle performance diagram of the flexible self-supporting Te nanotube composite electrode obtained in example 1 of the present invention, wherein the specific discharge capacity and capacity retention ratio of the electrode after 250 cycles at 1C rate are 237mAh g -1 And 104 percent, the self-supporting flexible electrode has higher specific discharge capacity and cycling stability.
Example 2
A preparation method of the flexible self-supporting tellurium nanotube composite electrode comprises the following four steps of S1, S2, S3 and S4:
s1, preparing a tellurium nanotube by a polymer-assisted solvothermal method:
0.25g of Na is taken 2 TeO 3 And 2.5g PVP dissolved in 125ml ultrapure water and stirred for 10min, then 50ml acetone is added and stirring is continued for 10min, and finally 15ml ammonia water and 7.5ml hydrazine hydrate are added and stirred for 20min. Transferring the obtained mixed solution into five parts, adding the five parts into a reaction kettle with five polytetrafluoroethylene inner containers with the capacity of 50ml, and transferring the reaction kettle into an oven with the temperature of 180 ℃ for reaction for 4 hours. And naturally cooling the reacted solution, pouring out supernatant, washing the obtained precipitate with ultrapure water for three times, centrifuging, collecting, and drying in a forced air drying oven at 80 ℃ for 8 hours to obtain the tellurium nanotubes. And detecting the phase and the morphology of the obtained product, wherein the average diameter of the tellurium nano tube is 60nm.
S2, preparing a tellurium nanotube dispersion liquid:
and adding 2mg of tellurium nanotubes into 20ml of absolute ethyl alcohol, and performing ultrasonic dispersion for 0.5h to obtain a tellurium nanotube dispersion liquid.
S3, preparing a nano-cellulose dispersion liquid:
adding 8g of nano-cellulose with solid content of 5% into 20ml of absolute ethyl alcohol solvent, and stirring at the rotating speed of 500r/min for 0.5h to obtain nano-cellulose dispersion liquid.
S4, preparing a flexible self-supporting tellurium nanotube composite electrode:
and uniformly adding the nano-cellulose dispersion liquid into a vacuum filtration device, and then uniformly adding the tellurium nanotube dispersion liquid into the vacuum filtration device for continuous filtration. And after the filtration, drying the film taken off from the filter paper in an air-blast drying oven at 80 ℃ for 12h to finally obtain the composite electrode with the lower layer being the nano-cellulose and the upper layer being the tellurium nanotubes.
And detecting the morphology and the electrochemical performance of the obtained flexible self-supporting tellurium nanotube composite electrode. FIG. 8 is the photographs before and after bending of the flexible self-supporting Te nanotube composite electrode obtained in example 2, and it can be seen that the obtained composite electrode has self-supportThe support structure has a smooth surface, the electrode has good flexibility, and the integrity of the electrode cannot be damaged in a bending state. Fig. 9 is an SEM image of the flexible self-supporting tellurium nanotube composite electrode obtained in example 2 of the present invention, in which the tellurium nanotubes are tightly interlaced to form an electrode active material layer. FIG. 10 is a cycle performance diagram of the flexible self-supporting Te nanotube composite electrode obtained in example 2 of the present invention, wherein the discharge specific capacity and the capacity retention rate of the electrode after 250 cycles under 1C rate are 223mAh g -1 And 146%, the self-supporting flexible electrode has better electrochemical performance.
Example 3
A preparation method of the flexible self-supporting tellurium nanotube composite electrode comprises the following four steps of S1, S2, S3 and S4:
s1, preparing a tellurium nanotube by a polymer-assisted solvothermal method:
0.25g of Na was taken 2 TeO 3 And 2g PVP dissolved in 50ml of ultrapure water and stirred for 10min, then 50ml of acetone is added and stirring is continued for 10min, and finally 7.5ml of ammonia water and 3.75ml of hydrazine hydrate are added and stirred for 20min. Transferring and dividing the obtained mixed solution into five parts, adding the five parts into five reaction kettles with 50ml capacity of polytetrafluoroethylene inner containers, and transferring the reaction kettles into an oven at 200 ℃ for reaction for 3 hours. And naturally cooling the reacted solution, pouring out supernatant, washing the obtained precipitate by adopting ultrapure water, centrifuging, repeating the washing and centrifuging for three times, collecting the precipitate, drying the precipitate in a 70 ℃ blast drying oven for 10 hours, and detecting the phase and the morphology of the obtained product, wherein the average diameter of the tellurium nano tube is 100nm.
S2, preparing a tellurium nanotube dispersion liquid:
adding 1mg of tellurium nanotubes into 20ml of absolute ethyl alcohol, and performing ultrasonic dispersion for 0.5h to obtain a tellurium nanotube dispersion liquid.
S3, preparing a nano-cellulose dispersion liquid:
adding 12g of nano-cellulose with solid content of 5% into 20ml of absolute ethanol solvent, and stirring at the rotating speed of 1000r/min for 0.3h to obtain nano-cellulose dispersion.
S4, preparing a flexible self-supporting tellurium nanotube composite electrode:
the nano-cellulose dispersion liquid is uniformly added into a vacuum filtration device, and then the tellurium nanotube dispersion liquid is uniformly added and continuously subjected to filtration. And after the filtration, drying the film taken off from the filter paper in an air-blast drying oven at 80 ℃ for 12h to finally obtain the composite electrode with the lower layer being the nano-cellulose and the upper layer being the tellurium nanotubes.
Example 4
A preparation method of the flexible self-supporting tellurium nanotube composite electrode comprises the following four steps of S1, S2, S3 and S4:
s1, preparing a tellurium nanotube by a polymer-assisted solvothermal method:
0.25g of Na was taken 2 TeO 3 And 3g PVP dissolved in 100ml ultrapure water and stirred for 10min, then 75ml acetone is added and stirring is continued for 10min, and finally 10ml ammonia water and 5ml hydrazine hydrate are added and stirred for 20min. Transferring the obtained mixed solution into five parts, adding the five parts into a reaction kettle with five polytetrafluoroethylene inner containers with the capacity of 50ml, and transferring the reaction kettle into an oven with the temperature of 190 ℃ for reaction for 3 hours. And naturally cooling the reacted solution, pouring out supernatant, washing the obtained precipitate by adopting ultrapure water, centrifuging, repeating the washing and centrifuging for three times, collecting the precipitate, drying the precipitate in a 70 ℃ blast drying oven for 10 hours, and detecting the phase and the morphology of the obtained product, wherein the average diameter of the tellurium nano tube is 70nm.
S2, preparing a tellurium nanotube dispersion liquid:
and adding 10mg of tellurium nanotubes into 20ml of absolute ethyl alcohol, and performing ultrasonic dispersion for 1 hour to obtain a tellurium nanotube dispersion liquid.
S3, preparing a nano-cellulose dispersion liquid:
adding 20g of nano-cellulose with solid content of 10% into 20ml of absolute ethanol solvent, and stirring at the rotating speed of 500r/min for 0.3h to obtain nano-cellulose dispersion.
S4, preparing a flexible self-supporting tellurium nanotube composite electrode:
and uniformly adding the nano-cellulose dispersion liquid into a vacuum filtration device, and then uniformly adding the tellurium nanotube dispersion liquid into the vacuum filtration device for continuous filtration. And after the filtration, drying the film taken off from the filter paper in a 70 ℃ blast drying oven for 16h to finally obtain the composite electrode with the lower layer being the nano-cellulose and the upper layer being the tellurium nanotubes.
Example 5
A preparation method of the flexible self-supporting tellurium nanotube composite electrode comprises the following four steps of S1, S2, S3 and S4:
s1, preparing a tellurium nanotube by a polymer-assisted solvothermal method:
0.25g of Na was taken 2 TeO 3 And 2.5g PVP dissolved in 200ml ultrapure water and stirred for 10min, then 100ml acetone is added and stirring is continued for 10min, and finally 20ml ammonia water and 10ml hydrazine hydrate are added and stirred for 20min. Transferring and dividing the obtained mixed solution into five parts, adding the five parts into five reaction kettles with 50ml capacity of polytetrafluoroethylene inner containers, and transferring the reaction kettles into an oven at 160 ℃ for reaction for 7 hours. And naturally cooling the solution after reaction, pouring out supernatant, washing the obtained precipitate with ultrapure water, centrifuging, repeating for three times, collecting the precipitate, drying in a forced air drying oven at 80 ℃ for 8 hours, and detecting the phase and morphology of the obtained product, wherein the average diameter of the tellurium nanotubes is 50nm.
S2, preparing a tellurium nanotube dispersion liquid:
and (3) adding 20mg of tellurium nanotubes into 20ml of absolute ethyl alcohol, and performing ultrasonic dispersion for 1 hour to obtain a tellurium nanotube dispersion liquid.
S3, preparing a nano-cellulose dispersion liquid:
adding 20g of nano-cellulose with solid content of 50% into 20ml of absolute ethyl alcohol solvent, and stirring for 1h at the rotating speed of 500r/min to obtain nano-cellulose dispersion liquid.
S4, preparing a flexible self-supporting tellurium nanotube composite electrode:
the nano-cellulose dispersion liquid is uniformly added into a vacuum filtration device, and then the tellurium nanotube dispersion liquid is uniformly added and continuously subjected to filtration. And after the filtration, drying the film taken off from the filter paper in a 70 ℃ blast drying oven for 16h to finally obtain the composite electrode with the lower layer being the nano-cellulose and the upper layer being the tellurium nanotubes.
Example 6
A preparation method of the flexible self-supporting tellurium nanotube composite electrode comprises the following four steps of S1, S2, S3 and S4:
s1, preparing a tellurium nanotube by a polymer-assisted solvothermal method:
0.25g of Na was taken 2 TeO 3 And 2g PVP dissolved in 250ml ultrapure water and stirred for 10min, then 25ml acetone is added and stirring is continued for 10min, and finally 30ml ammonia water and 15ml hydrazine hydrate are added and stirred for 20min. Transferring the obtained mixed solution into five parts, adding the five parts into a reaction kettle with five polytetrafluoroethylene inner containers with the capacity of 50ml, and transferring the reaction kettle into an oven with the temperature of 150 ℃ for reaction for 10 hours. And naturally cooling the solution after reaction, pouring out supernatant, washing the obtained precipitate with ultrapure water, centrifuging, repeating for three times, collecting the precipitate, drying in a forced air drying oven at 80 ℃ for 8 hours, and detecting the phase and morphology of the obtained product, wherein the average diameter of the tellurium nanotubes is 30nm.
S2, preparing a tellurium nanotube dispersion liquid:
and adding 40mg of tellurium nanotubes into 20ml of absolute ethyl alcohol, and performing ultrasonic dispersion for 1 hour to obtain a tellurium nanotube dispersion liquid.
S3, preparing a nano-cellulose dispersion liquid:
and (3) adding 20g of nano-cellulose with the solid content of 100% into 20ml of absolute ethanol solvent, and stirring at the rotating speed of 1000r/min for 0.5h to obtain nano-cellulose dispersion liquid.
S4, preparing a flexible self-supporting tellurium nanotube composite electrode:
and uniformly adding the nano-cellulose dispersion liquid into a vacuum filtration device, and then uniformly adding the tellurium nanotube dispersion liquid into the vacuum filtration device for continuous filtration. And after the suction filtration is finished, drying the film taken off from the filter paper in a forced air drying oven at the temperature of 80 ℃ for 12 hours to finally obtain the composite electrode with the lower layer of the nano-cellulose and the upper layer of the tellurium nanotubes.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (6)
1. A preparation method of a flexible self-supporting tellurium nanotube composite electrode is characterized by comprising the following steps of:
preparing a tellurium nanotube dispersion liquid: adding the tellurium nanotubes into absolute ethyl alcohol, and performing ultrasonic dispersion to obtain a tellurium nanotube dispersion liquid;
preparing flexible matrix dispersion liquid: adding the flexible matrix into absolute ethyl alcohol, and uniformly stirring to obtain a flexible matrix dispersion liquid;
preparing a flexible self-supporting tellurium nanotube composite electrode: and (3) performing suction filtration on the flexible matrix dispersion liquid by adopting a vacuum filtration method, adding the tellurium nanotube dispersion liquid, continuously performing suction filtration to obtain a composite film with a lower layer as a flexible matrix and an upper layer as a tellurium nanotube, drying, and cutting to obtain the flexible self-supporting tellurium nanotube composite electrode.
2. The flexible self-supporting tellurium nanotube composite electrode of claim 1, wherein in the step of preparing the tellurium nanotube dispersion, the method of preparing the tellurium nanotubes is as follows:
addition of Na to ultrapure water 2 TeO 3 And polyvinylpyrrolidone is stirred into a transparent solution, then acetone is added and uniformly mixed, ammonia water and hydrazine hydrate are added, the obtained mixed solution is transferred into a reaction kettle for hydrothermal reaction, the reactant is naturally cooled to room temperature, the supernatant is poured out, and the obtained precipitate is washed, centrifuged and dried to obtain the tellurium nanotube.
3. The flexible self-supporting tellurium nanotube composite electrode of claim 2, wherein in the step of preparing the tellurium nanotube dispersion, the Na is present in parts by weight 2 TeO 3 The dosage ratio of polyvinylpyrrolidone, ultrapure water, acetone, ammonia water and hydrazine hydrate is 1;
the reaction kettle is a reaction kettle with a polytetrafluoroethylene inner container, the hydrothermal reaction temperature is 150-200 ℃, and the reaction time is 3-10 h.
4. The flexible self-supporting tellurium nanotube composite electrode of claim 1, wherein in the step of preparing the tellurium nanotube dispersion, the concentration of the tellurium nanotube dispersion is 0.05-2 mg/ml, and the ultrasonic time is 0.5-1 h.
5. The flexible self-supporting tellurium nanotube composite electrode of claim 1, wherein in the step of preparing a flexible matrix dispersion, the concentration of the flexible matrix dispersion is 0.01-1 mg/ml;
the stirring is magnetic stirring, the rotating speed is 500-1000 r/min, and the stirring time is 0.5-1 h.
6. The flexible self-supporting tellurium nanotube composite electrode of claim 1, wherein in the step of preparing the flexible self-supporting tellurium nanotube composite electrode, the flexible matrix is nanocellulose, wherein the tellurium nanotubes comprise 80 to 95% of the total mass of the flexible self-supporting tellurium nanotube composite electrode and the nanocellulose comprises 5 to 20% of the total mass of the flexible self-supporting tellurium nanotube composite electrode.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010340734.XA CN111653757B (en) | 2020-04-26 | 2020-04-26 | Flexible self-supporting tellurium nanotube composite electrode, preparation method thereof and flexible battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010340734.XA CN111653757B (en) | 2020-04-26 | 2020-04-26 | Flexible self-supporting tellurium nanotube composite electrode, preparation method thereof and flexible battery |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111653757A CN111653757A (en) | 2020-09-11 |
CN111653757B true CN111653757B (en) | 2023-01-03 |
Family
ID=72349337
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010340734.XA Expired - Fee Related CN111653757B (en) | 2020-04-26 | 2020-04-26 | Flexible self-supporting tellurium nanotube composite electrode, preparation method thereof and flexible battery |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111653757B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114400340B (en) * | 2022-01-19 | 2023-12-22 | 中原工学院 | Nitrogen-sulfur co-doped carbon nanotube composite material and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102086025A (en) * | 2011-01-07 | 2011-06-08 | 中国科学技术大学 | Preparation method of one-dimensional (1D) flexible nano-material assembly body |
CN105810446A (en) * | 2016-03-16 | 2016-07-27 | 杭州禹净环境科技有限公司 | Preparation method for molybdenum disulfide nanosheet loaded tellurium nanotube |
CN108390064A (en) * | 2018-01-19 | 2018-08-10 | 同济大学 | A kind of graphene-based flexible self-supporting mixed gel electrode and preparation method thereof |
CN109285991A (en) * | 2018-10-17 | 2019-01-29 | 广东邦普循环科技有限公司 | A kind of preparation method and application of flexible compound electrode |
CN110449169A (en) * | 2019-07-04 | 2019-11-15 | 中山大学 | A kind of semi-metallic Te nano wire/graphene hydrogel composite material and its preparation method and application |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104934610B (en) * | 2015-05-06 | 2017-11-10 | 南昌航空大学 | A kind of lithium ion battery self-supporting flexible composite electrode material preparation method |
CN110752353B (en) * | 2019-09-19 | 2022-05-13 | 广东工业大学 | Flexible self-supporting tin diselenide/carbon nano tube composite film electrode material and preparation method and application thereof |
-
2020
- 2020-04-26 CN CN202010340734.XA patent/CN111653757B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102086025A (en) * | 2011-01-07 | 2011-06-08 | 中国科学技术大学 | Preparation method of one-dimensional (1D) flexible nano-material assembly body |
CN105810446A (en) * | 2016-03-16 | 2016-07-27 | 杭州禹净环境科技有限公司 | Preparation method for molybdenum disulfide nanosheet loaded tellurium nanotube |
CN108390064A (en) * | 2018-01-19 | 2018-08-10 | 同济大学 | A kind of graphene-based flexible self-supporting mixed gel electrode and preparation method thereof |
CN109285991A (en) * | 2018-10-17 | 2019-01-29 | 广东邦普循环科技有限公司 | A kind of preparation method and application of flexible compound electrode |
CN110449169A (en) * | 2019-07-04 | 2019-11-15 | 中山大学 | A kind of semi-metallic Te nano wire/graphene hydrogel composite material and its preparation method and application |
Non-Patent Citations (1)
Title |
---|
Elastic Carbon Nanotube Aerogel Meets Tellurium Nanowires: A Binder- and Collector-Free Electrode for Li-Te Batteries;Jie Xu , Sen Xin,Jian-Wei Liu,Jin-Long Wang,Yong Lei,and Shu-Hon;《ADVANCED FUNCTIONAL MATERIALS》;20160511;3580-3588 * |
Also Published As
Publication number | Publication date |
---|---|
CN111653757A (en) | 2020-09-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9923200B2 (en) | Method for making sulfur-graphene composite material | |
CN105609740B (en) | A kind of silicon alloy complex microsphere and preparation method and application | |
Ye et al. | Facile preparation of graphene nanosheets encapsulated Fe3O4 octahedra composite and its high lithium storage performances | |
CN110943216B (en) | Preparation method of cobalt-iron bimetallic selenide sodium-ion battery cathode material | |
JP2011048992A (en) | Carbon material, electrode material, and lithium ion secondary battery negative electrode material | |
JP2016004786A (en) | CARBON NANOTUBE-METAL NANOCOMPOSITE AS FLEXIBLE, SELF-SUPPORTING, BINDER FREE HIGH PERFORMANCE ANODE FOR Li ION BATTERY | |
WO2012071914A1 (en) | Negative active material, method for preparing the same and lithium ion battery comprising the same | |
JP2011057541A (en) | Carbon material, electrode material, and negative-electrode material for lithium-ion secondary battery | |
CN108493425B (en) | Preparation method of Sn4P3 nanoparticle sodium ion battery cathode material coated by mesoporous carbon nanotube | |
CN110168780A (en) | Porous no binder electrode film | |
Xiang et al. | Synergistic capture and conversion of polysulfides in cathode composites with multidimensional framework structures | |
CN115663151B (en) | Pre-magnesium silica composite material, silicon-based anode material, preparation method and secondary battery | |
CN109192951B (en) | Preparation method and application of nanometer flower-shaped spherical cobalt disulfide composite material | |
CN115763717A (en) | Sodium ion battery positive electrode material, preparation method thereof, sodium ion battery positive electrode piece and sodium ion battery | |
CN112421133A (en) | Graphene/functionalized metal-organic framework material composite intercalation and preparation method and application thereof | |
CN110085823B (en) | Nano composite negative electrode material and preparation method and application thereof | |
CN111653757B (en) | Flexible self-supporting tellurium nanotube composite electrode, preparation method thereof and flexible battery | |
CN108390046B (en) | Preparation method of rod-shaped α -ferric oxide/GN lithium battery negative electrode material | |
CN113571681A (en) | Hollow titanium dioxide/nickel/carbon composite material and preparation method and application thereof | |
CN111628176B (en) | Multi-component three-dimensional conductive carbon network, self-supporting composite electrode, and preparation methods and applications thereof | |
Gong et al. | Yolk-shell silicon/carbon composites prepared from aluminum-silicon alloy as anode materials for lithium-ion batteries | |
CN110504450A (en) | A kind of preparation method of the multi-stage porous carbon material of Heteroatom doping and the application in cathode of lithium battery slurry | |
TW202030912A (en) | Electrode material for electrical storage device, electrode, electrical storage device, electrical equipment, and method for manufacturing electrode material for electrical storage device | |
CN115663137A (en) | Metal organic framework material coated silicon ball lithium ion battery cathode material and preparation method thereof | |
CN111755696B (en) | Composite negative electrode material, preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20230103 |
|
CF01 | Termination of patent right due to non-payment of annual fee |