CN106784771A - A kind of preparation method and system of zinc antimony alloy composite negative pole material - Google Patents
A kind of preparation method and system of zinc antimony alloy composite negative pole material Download PDFInfo
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- CN106784771A CN106784771A CN201710182921.8A CN201710182921A CN106784771A CN 106784771 A CN106784771 A CN 106784771A CN 201710182921 A CN201710182921 A CN 201710182921A CN 106784771 A CN106784771 A CN 106784771A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 33
- 229910001245 Sb alloy Inorganic materials 0.000 title claims abstract description 29
- 239000002140 antimony alloy Substances 0.000 title claims abstract description 29
- CZJCMXPZSYNVLP-UHFFFAOYSA-N antimony zinc Chemical compound [Zn].[Sb] CZJCMXPZSYNVLP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052787 antimony Inorganic materials 0.000 claims description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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
- H01M4/42—Alloys based on zinc
-
- 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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
Abstract
The invention discloses a kind of preparation method and system of zinc antimony alloy composite negative pole material, the system includes carbon material preparation facilities and composite preparation facilities two parts, carbon material preparation facilities includes the stirred tank, carbide furnace and the graphitizing furnace that are sequentially connected, composite preparation facilities includes the batch mixer, high energy ball mill and the discharge plasma sintering machine that are sequentially connected, wherein, graphitizing furnace is connected with batch mixer.With the carbon material after specially treated be combined with each other zinc antimony alloy by the present invention, and the composite negative pole material for preparing has splendid cyclical stability, and electric property is good.Preparation system of the invention includes the carbon material preparation facilities and composite preparation facilities two parts that are sequentially connected, and continuous production substantially increases production efficiency.
Description
Technical field
The present invention relates to a kind of alloy material, and in particular to a kind of preparation method of zinc antimony alloy composite negative pole material and be
System.Belong to nonferrous materials processing technique field.
Background technology
The energy is the important substance basis of human social development, but, with fossil energies such as coal, oil and natural gas
Storage fall sharply, the resource exhaustion pressure that human society faces is increasing, therefore, how to improve energy utilization rate and exploitation profit
The common objective of national governments and scientific research personnel is had become with regenerative resource.
Battery is storage and the reforming unit of a kind of chemical energy and electric energy.Wherein, lithium ion battery because its have voltage it is high,
Specific energy is high, discharge and recharge long lifespan, memory-less effect, pollution-free, operating temperature range wide, quick charge, self-discharge rate are low and
Safe and reliable the advantages of, have become the desirable chemical power supply of modern communication and portable type electronic product etc..
Generally using graphite material as negative pole, its theoretical specific capacity is only current commercialized lithium ion battery
372mAh/g, and there is graphite linings peeling phenomenon during fast charging and discharging, cause obvious capacity attenuation.And, fast
Li dendrite phenomenon, these factors is easily produced all seriously to constrain answering in power lithium-ion battery in fast charge and discharge process
With.Therefore, using other materials instead of graphite cathode be current lithium ion battery research emphasis and difficult point where.
The content of the invention
The purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, there is provided a kind of zinc antimony alloy composite negative pole material
Preparation method.
Present invention also offers a kind of corresponding preparation system of zinc antimony alloy composite negative pole material of above-mentioned preparation method.
To achieve the above object, the present invention uses following technical proposals：
A kind of preparation method of zinc antimony alloy composite negative pole material, comprises the following steps that：
(1) by graphite powder and epoxy resin powder according to mass ratio 1：0.5~0.8 add stirred tank in, with 20~25 DEG C/
The speed of min is warming up to 450~550 DEG C, stirs 4~5 hours；It is transferred in carbide furnace, under nitrogen protection, 1600~1700 DEG C
Insulation 2~3 hours, is transferred in graphitizing furnace, is warming up to 2500~2600 DEG C and is incubated 12~15 hours, obtains carbon material；
(2) by step (1) gained carbon material and zinc powder, antimony powder according to mol ratio 1：2~3：3~4 mix in batch mixer
Uniformly, be transferred to high energy ball mill, grind 10~20 hours, be transferred to discharge plasma sintering machine, in 30~1000MPa and
Sintered 5~8 minutes under the conditions of 200~600 DEG C, obtain final product zinc antimony alloy composite negative pole material.
Preferably, in step (1), the average grain diameter of graphite powder is 10~15 μm, average grain diameter≤5 μ of epoxy resin powder
m。
Preferably, in step (2), after carbon material, zinc powder and antimony powder are well mixed, the NaOH using 23w.t.% is molten
Liquid is fully washed.
Preferably, nitrogen protection is filled with step (2) during grinding.
A kind of corresponding preparation system of zinc antimony alloy composite negative pole material of above-mentioned preparation method, including carbon material prepares dress
Put includes the stirred tank, carbide furnace and the stone that are sequentially connected with composite preparation facilities two parts, the carbon material preparation facilities
Mo Hualu, the composite preparation facilities includes the batch mixer, high energy ball mill and the discharge plasma sintering machine that are sequentially connected,
Wherein, graphitizing furnace is connected with batch mixer.
Preferably, alkali cleaning pond is additionally provided between the batch mixer and high energy ball mill.
Further preferably, several spray heads, spray head and sodium hydroxide solution storage tank are provided with above the alkali cleaning pond
Connection.
Beneficial effects of the present invention：
With the carbon material after specially treated be combined with each other zinc antimony alloy by the present invention, the composite negative pole material for preparing
With splendid cyclical stability, electric property is good.Preparation system of the invention includes the carbon material preparation facilities being sequentially connected
With composite preparation facilities two parts, continuously production, substantially increases production efficiency.
Brief description of the drawings
Fig. 1 is preparation system structural representation of the invention；
Wherein, 1 is carbon material preparation facilities, and 2 is composite preparation facilities, and 11 is stirred tank, and 12 is carbide furnace, and 13 are
Graphitizing furnace, 21 is batch mixer, and 22 is alkali cleaning pond, and 23 is high energy ball mill, and 24 is discharge plasma sintering machine.
Specific embodiment
The present invention will be further elaborated with reference to the accompanying drawings and examples, it should explanation, and the description below is only
It is, in order to explain the present invention, its content not to be defined.
Embodiment 1：
A kind of preparation method of zinc antimony alloy composite negative pole material, comprises the following steps that：
(1) by graphite powder and epoxy resin powder according to mass ratio 1：In 0.5 addition stirred tank 11, with the speed of 20 DEG C/min
450 DEG C are warming up to, are stirred 4 hours；It is transferred in carbide furnace 12, under nitrogen protection, 1600 DEG C are incubated 2 hours, are transferred to graphite
Change in stove 13, be warming up to 2500 DEG C and be incubated 12 hours, obtain carbon material；
(2) by step (1) gained carbon material and zinc powder, antimony powder according to mol ratio 1：2：3 are well mixed in batch mixer 21,
High energy ball mill 23 is transferred to, grinding 10 hours (being filled with nitrogen protection) is transferred to discharge plasma sintering machine 24, in 30MPa
With 200 DEG C under the conditions of sinter 5 minutes, obtain final product zinc antimony alloy composite negative pole material.
In step (1), the average grain diameter of graphite powder is 10 μm, average grain diameter≤5 μm of epoxy resin powder.
In step (2), after carbon material, zinc powder and antimony powder are well mixed, carried out using the sodium hydroxide solution of 23w.t.%
Fully washing.
As shown in figure 1, a kind of preparation system of zinc antimony alloy composite negative pole material, including carbon material preparation facilities 1 and multiple
The two parts of condensation material preparation facilities 2, carbon material preparation facilities 1 includes the stirred tank 11, carbide furnace 12 and the graphitization that are sequentially connected
Stove 13, composite preparation facilities 2 includes the batch mixer 21, high energy ball mill 23 and the discharge plasma sintering machine that are sequentially connected
24, wherein, graphitizing furnace 13 is connected with batch mixer 21.
Alkali cleaning pond 22 is additionally provided between batch mixer 21 and high energy ball mill 23.The top in alkali cleaning pond 22 is provided with several sprays
Head, spray head is connected with sodium hydroxide solution storage tank.
Embodiment 2：
A kind of preparation method of zinc antimony alloy composite negative pole material, comprises the following steps that：
(1) by graphite powder and epoxy resin powder according to mass ratio 1：In 0.8 addition stirred tank 11, with the speed of 25 DEG C/min
550 DEG C are warming up to, are stirred 5 hours；It is transferred in carbide furnace 12, under nitrogen protection, 1700 DEG C are incubated 3 hours, are transferred to graphite
Change in stove 13, be warming up to 2600 DEG C and be incubated 15 hours, obtain carbon material；
(2) by step (1) gained carbon material and zinc powder, antimony powder according to mol ratio 1：3：4 are well mixed in batch mixer 21,
High energy ball mill 23 is transferred to, grinding 20 hours (being filled with nitrogen protection) is transferred to discharge plasma sintering machine 24,
Sintered 8 minutes under the conditions of 1000MPa and 600 DEG C, obtain final product zinc antimony alloy composite negative pole material.
In step (1), the average grain diameter of graphite powder is 15 μm, average grain diameter≤5 μm of epoxy resin powder.
In step (2), after carbon material, zinc powder and antimony powder are well mixed, carried out using the sodium hydroxide solution of 23w.t.%
Fully washing.
A kind of preparation system of zinc antimony alloy composite negative pole material, with embodiment 1.
Embodiment 3：
A kind of preparation method of zinc antimony alloy composite negative pole material, comprises the following steps that：
(1) by graphite powder and epoxy resin powder according to mass ratio 1：In 0.5 addition stirred tank 11, with the speed of 25 DEG C/min
450 DEG C are warming up to, are stirred 5 hours；It is transferred in carbide furnace 12, under nitrogen protection, 1600 DEG C are incubated 3 hours, are transferred to graphite
Change in stove 13, be warming up to 2500 DEG C and be incubated 15 hours, obtain carbon material；
(2) by step (1) gained carbon material and zinc powder, antimony powder according to mol ratio 1：2：4 are well mixed in batch mixer 21,
High energy ball mill 23 is transferred to, grinding 10 hours (being filled with nitrogen protection) is transferred to discharge plasma sintering machine 24,
Sintered 8 minutes under the conditions of 1000MPa and 200 DEG C, obtain final product zinc antimony alloy composite negative pole material.
In step (1), the average grain diameter of graphite powder is 10 μm, average grain diameter≤5 μm of epoxy resin powder.
In step (2), after carbon material, zinc powder and antimony powder are well mixed, carried out using the sodium hydroxide solution of 23w.t.%
Fully washing.
A kind of preparation system of zinc antimony alloy composite negative pole material, with embodiment 1.
Embodiment 4：
A kind of preparation method of zinc antimony alloy composite negative pole material, comprises the following steps that：
(1) by graphite powder and epoxy resin powder according to mass ratio 1：In 0.8 addition stirred tank 11, with the speed of 20 DEG C/min
550 DEG C are warming up to, are stirred 4 hours；It is transferred in carbide furnace 12, under nitrogen protection, 1700 DEG C are incubated 2 hours, are transferred to graphite
Change in stove 13, be warming up to 2600 DEG C and be incubated 12 hours, obtain carbon material；
(2) by step (1) gained carbon material and zinc powder, antimony powder according to mol ratio 1：3：3 are well mixed in batch mixer 21,
High energy ball mill 23 is transferred to, grinding 20 hours (being filled with nitrogen protection) is transferred to discharge plasma sintering machine 24, in 30MPa
With 600 DEG C under the conditions of sinter 5 minutes, obtain final product zinc antimony alloy composite negative pole material.
In step (1), the average grain diameter of graphite powder is 15 μm, average grain diameter≤5 μm of epoxy resin powder.
In step (2), after carbon material, zinc powder and antimony powder are well mixed, carried out using the sodium hydroxide solution of 23w.t.%
Fully washing.
A kind of preparation system of zinc antimony alloy composite negative pole material, with embodiment 1.
Embodiment 5：
A kind of preparation method of zinc antimony alloy composite negative pole material, comprises the following steps that：
(1) by graphite powder and epoxy resin powder according to mass ratio 1：In 0.7 addition stirred tank 11, with the speed of 22 DEG C/min
500 DEG C are warming up to, are stirred 4.5 hours；It is transferred in carbide furnace 12, under nitrogen protection, 1650 DEG C are incubated 2.5 hours, are transferred to
In graphitizing furnace 13, it is warming up to 2550 DEG C and is incubated 13 hours, obtains carbon material；
(2) by step (1) gained carbon material and zinc powder, antimony powder according to mol ratio 1：2.5：3.5 mix in batch mixer 21
Uniformly, high energy ball mill 23 is transferred to, grinding 15 hours (being filled with nitrogen protection) is transferred to discharge plasma sintering machine 24,
Sintered 7 minutes under the conditions of 500MPa and 400 DEG C, obtain final product zinc antimony alloy composite negative pole material.
In step (1), the average grain diameter of graphite powder is 12 μm, average grain diameter≤5 μm of epoxy resin powder.
In step (2), after carbon material, zinc powder and antimony powder are well mixed, carried out using the sodium hydroxide solution of 23w.t.%
Fully washing.
A kind of preparation system of zinc antimony alloy composite negative pole material, with embodiment 1.
Test example
The composite negative pole material of the gained of embodiment 1~5 is evenly applied to be made electrode on Copper Foil, use metallic sodium piece for
Positive pole, electrolyte is the NaClO of 1mol/L4(volume ratio is 1 to/EC-DMC：1), polypropylene microporous film (Celgard 2300)
It is barrier film, is assembled into sodium ion half-cell, test loop stability, i.e., under 0.1C multiplying powers, in 0.01~1.8V voltage ranges
Long-time circulate 50 times circulation after specific capacity, the results are shown in Table 1.
The cyclical stability test result of table 1.
By table 1 it could be assumed that, composite negative pole material of the invention has splendid cyclical stability.
Although above-mentioned be described with reference to accompanying drawing to specific embodiment of the invention, not to present invention protection model
The limitation enclosed, on the basis of technical scheme, those skilled in the art do by need not paying creative work
The various modifications or deformation for going out are still within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of zinc antimony alloy composite negative pole material, it is characterised in that comprise the following steps that：
(1) by graphite powder and epoxy resin powder according to mass ratio 1：In 0.5~0.8 addition stirred tank, with 20~25 DEG C/min's
Speed is warming up to 450~550 DEG C, stirs 4~5 hours；It is transferred in carbide furnace, under nitrogen protection, 1600~1700 DEG C of insulations 2
~3 hours, it is transferred in graphitizing furnace, is warming up to 2500~2600 DEG C and is incubated 12~15 hours, obtains carbon material；
(2) by step (1) gained carbon material and zinc powder, antimony powder according to mol ratio 1：2~3：3~4 are well mixed in batch mixer,
Be transferred to high energy ball mill, grind 10~20 hours, be transferred to discharge plasma sintering machine, 30~1000MPa and 200~
Sintered 5~8 minutes under the conditions of 600 DEG C, obtain final product zinc antimony alloy composite negative pole material.
2. preparation method according to claim 1, it is characterised in that in step (1), the average grain diameter of graphite powder for 10~
15 μm, average grain diameter≤5 μm of epoxy resin powder.
3. preparation method according to claim 1, it is characterised in that in step (2), the mixing of carbon material, zinc powder and antimony powder
After uniform, fully washed using the sodium hydroxide solution of 23w.t.%.
4. preparation method according to claim 1, it is characterised in that be filled with nitrogen protection in step (2) during grinding.
5. the corresponding a kind of preparation system of zinc antimony alloy composite negative pole material of preparation method any one of Claims 1 to 4
System, it is characterised in that including carbon material preparation facilities and composite preparation facilities two parts, the carbon material preparation facilities bag
Include stirred tank, carbide furnace and the graphitizing furnace being sequentially connected, batch mixer that the composite preparation facilities includes being sequentially connected,
High energy ball mill and discharge plasma sintering machine, wherein, graphitizing furnace is connected with batch mixer.
6. preparation system according to claim 5, it is characterised in that be additionally provided between the batch mixer and high energy ball mill
Alkali cleaning pond.
7. preparation system according to claim 6, it is characterised in that several sprays are provided with above the alkali cleaning pond
Head, spray head is connected with sodium hydroxide solution storage tank.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112768646A (en) * | 2020-12-04 | 2021-05-07 | 杭州电子科技大学 | Method for preparing antimony-based alloy/nitrogen-doped carbon composite porous material by self-template method, composite porous material and application |
| CN115986099A (en) * | 2022-12-15 | 2023-04-18 | 天津大学 | Three-dimensional carbon skeleton zinc composite material for dendrite-free zinc metal battery cathode and preparation method thereof |
| CN116014093A (en) * | 2022-12-15 | 2023-04-25 | 天津大学 | High-conductivity functional group heterogeneous-phase connection material at zinc grain boundary and preparation method thereof |
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| KR20150052476A (en) * | 2013-11-06 | 2015-05-14 | 금오공과대학교 산학협력단 | Method for manufacturing binary metal compound composite, rechargeable battery comprising the same |
| CN206639862U (en) * | 2017-03-24 | 2017-11-14 | 南昌专腾科技有限公司 | A kind of preparation system of zinc antimony alloy composite negative pole material |
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| CN112768646A (en) * | 2020-12-04 | 2021-05-07 | 杭州电子科技大学 | Method for preparing antimony-based alloy/nitrogen-doped carbon composite porous material by self-template method, composite porous material and application |
| CN115986099A (en) * | 2022-12-15 | 2023-04-18 | 天津大学 | Three-dimensional carbon skeleton zinc composite material for dendrite-free zinc metal battery cathode and preparation method thereof |
| CN116014093A (en) * | 2022-12-15 | 2023-04-25 | 天津大学 | High-conductivity functional group heterogeneous-phase connection material at zinc grain boundary and preparation method thereof |
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