CN104393300B - The electrode material of lithium ion battery and its application in lithium ion battery - Google Patents
The electrode material of lithium ion battery and its application in lithium ion battery Download PDFInfo
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- CN104393300B CN104393300B CN201410542330.3A CN201410542330A CN104393300B CN 104393300 B CN104393300 B CN 104393300B CN 201410542330 A CN201410542330 A CN 201410542330A CN 104393300 B CN104393300 B CN 104393300B
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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 provides a kind of electrode material of lithium ion battery, the electrode material is included in metal organic framework and the metal organic framework comprising at least one ribavirin, and at least one metal ion.Experiment is confirmed, the lithium ion cell electrode has good charge and discharge cycles stability, after repeatedly circulation, metallo-organic framework in electrode material is intact, the specific discharge capacity of battery tends towards stability and maintains high value, amplitude of variation is smaller, therefore is a kind of electrode material with applications well prospect.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of lithium ion battery includes metal organic framework
Electrode material, its application in lithium ion battery, and use the lithium ion battery of the electrode material.
Background technology
Metal-organic framework materials (Metal-Organic Frameworks, abbreviation MOFs) are by metal and organic matched somebody with somebody
A kind of inorganic material with mesh skeleton that body is formed by coordination, its be mainly characterized by with very high ratio surface,
Pore volume and adjustable aperture.The research to MOFs materials is concentrated mainly on gas absorption separation or stored at present, and catalyst is carried
The gas absorption separation in the fields such as body, pharmaceutical carrier and magnetic, wherein MOFs materials or storage performance are studied the most extensive.
MOFs materials are easy to ion to be transmitted in its structure due to the duct with high-ratio surface and rule, while its
Surface also adsorbable ion so that it is expected to the electrode material applied to lithium ion battery.At present using MOFs materials as lithium from
The existing relevant report of sub-electrode material.For example, J.Chen etc. is in document：J.Power Sources 160 (2006), 542-
The porous organo-metallic skeleton material MOF-177 based on 1,3,5- tri- (4- carboxyl phenyls) benzene has been recorded in 547 in lithium-ion electric
Application in the negative material of pond.Although the MOF-177 negative materials have good initial specific capacities, the storage of its lithium ion
Capacity but drastically declines with the increase of discharge and recharge number of times.And for example, the A of CN 102893434 are disclosed based on dihydroxy dicarboxyl
The metal-organic framework materials of acid and its application as electrode of lithium cell, its specific capacity is not in 175-260mAh/g, but not
There is the cycle performance for disclosing the lithium battery.
The stability of MOFs materials is always the problem of researchers pay close attention to, and is also one of significant challenge.But, for example
The metal-organic framework materials such as MOF-5, MOF-177 expose a period of time under air, and structure will be destroyed.On the other hand, it is electric
Chemical cell, such as lithium ion battery are during discharge and recharge, due to there is giving for electronics, this it is also possible that metal it is organic
Reduction reaction occurs for framework material, and causes the destruction of MOFs material structures.However, preparing electrochemical cell electrode, such as
During lithium ion cell electrode, exposure under air is difficult to avoid that.
The content of the invention
For the above-mentioned state of the art, the present inventor has found after many experiments exploratory development：From metal organic framework
Material as lithium ion battery electrode material when, when in the skeleton of metal-organic framework materials comprising at least one ribavirin,
And during at least one metal ion, battery has good charge and discharge cycles stability, after repeatedly circulation, electrode material
Structure it is intact, the specific discharge capacity of battery tends towards stability and maintains high value, and amplitude of variation is smaller.
That is, the technical scheme that provides of the present invention is：A kind of electrode material of lithium ion battery, described electrode material is included
Metal-organic framework materials, it is characterized in that：Comprising at least one ribavirin in described metal organic framework, and it is at least one
Metal ion.
Described ribavirin includes but is not limited to imidazoles, benzimidazole, aminobenzimidazole and its derivative.
Described metal ion includes but is not limited to zinc, cobalt ions etc..
Preferably, described metal-organic framework materials are the metal-organic framework materials of functionalization, wrapped in its skeleton
Metal ion Zn2+Or Co2+, and imidazoles and aminobenzimidazole.The preparation of the metal-organic framework materials of the functionalization
Method is preferably as follows：
To contain the presoma of imidazoles and aminobenzimidazole as reaction part, with containing Zn2+Soluble-salt or
Contain Co2+Soluble-salt carry out solvent thermal reaction in organic solvent, obtain amino functional ZIF types of metals organic backbones
Porous material crude product, it is then that amino functional ZIF types of metals organic backbone porous material crude products is scrubbed, dry
And heating, vacuum activation, obtain pure amino functional ZIF types of metals organic backbone porous materials.
Wherein, the presoma containing imidazoles and aminobenzimidazole is included containing imidazoles and aminobenzimidazole
Simple substance, hydrate or metal salt compound.
Described contains Zn2+Solvable zinc salt include but is not limited to zinc nitrate hydrate, zinc acetate hydrate, zinc chloride,
Mixture more than one or both of hydrate of zinc sulfata etc..
Described contains Co2+Solvable zinc salt include but is not limited to cobalt nitrate hydrate, cobalt acetate hydrate, cobalt chloride,
Mixture more than one or both of cobaltous sulfate hydrate etc..
Described organic solvent includes but is not limited to N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, N- diethyls
Base formamide equal solvent.
Preferably, the reaction temperature of described solvent thermal reaction is 90~150 DEG C.
Preferably, the reaction time of described solvent thermal reaction is 12~96 hours.
It is experimentally confirmed that well-regulated using the metal organic framework porous material tool of the functionalization made from the above method
ZIF crystal structures, i.e. zeolite imidazole ester skeleton structure, are porous crystalline materials.Contain metal ion, imidazoles and amino in skeleton
The crosslinking of benzimidazole, imidazoles and aminobenzimidazole is connected on metal, forms a kind of framework of zeolite imidazole esters type.
That is, in lithium ion battery, the present invention is used as electrode material from ribavirin metalloid organic framework material.Experiment
Confirm, the electrode material of the lithium ion battery has following unexpected beneficial effect：
(1) there is good specific discharge capacity
The electrode material of the lithium ion battery of the present invention has good specific discharge capacity, not only its first discharge specific capacity
Height, and after n times (described N is more than or equal to 10) charge and discharge cycles, or even more than 100th circulation, with 100mA/g's
When current density is tested in blue electrical measurement test system, its specific discharge capacity circulated every time is above 100mAhg-1；
(2) there is stable specific discharge capacity
After n times ring, described N is more than or equal to 10, the electric discharge specific volume of the electrode material of lithium ion battery of the invention
Amount tends towards stability, i.e. compared with the specific discharge capacity that n-th is measured, since n-th circulation, every time the electric discharge ratio in circulation
Capacity maintains essentially in more than the 95% of n-th specific discharge capacity, or even maintains more than 99%, amplitude of variation very little, therefore
With stable specific discharge capacity；
(3) there is excellent structural stability
After M times circulates, the gold that described M is more than or equal in 100, lithium ion battery electrode material of the invention
Category it is organic framework structured remain in that it is intact.
Brief description of the drawings
Fig. 1 is the powder xrd pattern of obtained ZIF-4 in the embodiment of the present invention 1；
Fig. 2 is the powder xrd pattern of obtained ZIF-62 in the embodiment of the present invention 2；
The single crystal X-ray diffraction figure result that Fig. 3 is amino functional ZIF-62 made from the embodiment of the present invention 3 is parsed
Obtained crystal structure figure；
Fig. 4 is the minimum repeat unit in crystal structure figure shown in Fig. 3；
Fig. 5 is the XRD curves of amino functional ZIF-62 made from the embodiment of the present invention 3；
Fig. 6 is the amino functional ZIF- after 200 loop tests of lithium ion half-cell made from the embodiment of the present invention 3
The XRD of 62 materials and its XRD before testing comparison diagram.
Embodiment
The present invention is described in further detail with embodiment below in conjunction with accompanying drawing, it should be pointed out that reality as described below
Apply example to be intended to be easy to the understanding of the present invention, and do not play any restriction effect to it.
Embodiment 1：
In the present embodiment, the storage lithium performance of electrode material is tested using half-cell.Half-cell is main by positive electrode, negative electricity
Pole, barrier film, electrolyte composition.
Negative pole is lithium piece；
Just extremely mixing material, is made up of ZIF-4, Super-p, PVDF；
Barrier film is Celgard 2400；
Electrolyte is 1mol/L lithium hexafluoro phosphates (LiPF in electrolyte6), solvent is that volume ratio is 1：1：1 FEC (fluoro
Ethylene carbonate)：DMC (dimethyl carbonate)：EMC (methyl ethyl carbonate fat) mixed solvent.
Wherein, ZIF-4 prepare it is as follows：
By 0.9g Zn (NO3)·6H2O, 0.63g C3H4N2(imidazoles) is dissolved in 40ml DMFs, stirring
Moved into after uniform and solvent thermal reaction is carried out in polytetrafluoro reactor, reaction temperature is 130 DEG C, reflecting time is 3 days.Reaction terminates
Afterwards, room temperature is naturally cooled to, reactor is opened, collection ZIF-4 white crystals after solvent are outwelled.With N., N-dimethylformamide leaching
Steep ZIF-4 crystal 1 day, DMF solvent is outwelled afterwards, use methanol solvate immersion ZIF-4 crystal instead 1 day, outwell
Methanol solvate, after spontaneously drying at room temperature, carries out 220 DEG C of vacuum activating 24h.
The XRD of ZIF-4 obtained above powder is as shown in figure 1, it can be seen that the ZIF-4 materials and document：
The material reported in Science 319, (2008), 939-943 is consistent.
Preparing for positive pole is as follows：
(1) by ZIF-4,80 DEG C of vacuum drying remove the moisture content wherein contained for 12 hours in vacuum drying chamber, in mass ratio
ZIF-4：Super-p：PVDF=7：2：1 ratio is added appropriate 1-METHYLPYRROLIDONE solvent ball milling and is well mixed for 5 hours；
(2) slurry is coated uniformly on copper foil surface using scraper, 80 DEG C of vacuum drying oven is dried 12 hours, copper foil is cut into
A diameter of 14cm pole piece, after again pass through tabletting, dry, weigh etc. step be put into the glove box containing inert gas assemble electricity
Pond.
With 100mA/g current density in the chemical property of the above-mentioned lithium ion half-cell of blue electrical testing system testing, survey
Test result is as shown in table 1.
From the result shown in table 1 can be seen that battery using ZIF-4 as electrode active material not only have it is excellent first
Charging and discharging capacity, and after 10 charge and discharge cycles, its specific discharge capacity remains within higher value, and tends to
Stable, i.e., amplitude of variation is smaller.For example, the specific discharge capacity of the 10th charge and discharge cycles reaches 143mAh/g, the 50th charge and discharge
The specific discharge capacity of electricity circulation reaches 147.1mAh/g, and the specific discharge capacity of the 100th charge and discharge cycles even remains able to reach
To 141.9mAh/g.
Also, after tested, after 100 loop tests, ZIF-4 XRD and its XRD basic one before testing
Cause, this explanation ZIF-4 structure in the electrochemical environment of lithium battery will not cave in, therefore be conducive to battery to have good electrification
Learn stability.
Embodiment 2：
In the present embodiment, the structure of lithium ion battery is substantially the same manner as Example 1, except that mixing material is by ZIF-
62nd, Super-p, PVDF are constituted.
Wherein, ZIF-62 prepare it is as follows：
By 3.0g Zn (NO3)·6H2O、1.4g C3H4N2(imidazoles) and 1.18g C7H6N2(benzimidazole) is dissolved in 200ml
Moved into DMF, after stirring in polytetrafluoro reactor and carry out solvent thermal reaction, reaction temperature is 130
DEG C, the reaction time is 3 days.After reaction terminates, room temperature is naturally cooled to, reactor is opened, collection ZIF-62 after solvent is outwelled white
Color crystal.With N., N-dimethylformamide immersion ZIF-62 crystal 1 day outwells DMF solvent, uses first instead afterwards
Alcoholic solvent immersion ZIF-62 crystal 1 day, outwells methanol solvate, after spontaneously drying at room temperature, carries out 220 DEG C of vacuum activating 24h.
The XRD of ZIF-62 obtained above powder is as shown in Fig. 2 it can be seen that the ZIF-62 materials and text
Offer：The material structure reported in Science 319, (2008), 939-943 is consistent.
The preparation method of positive pole is substantially the same manner as Example 1, except that replacing ZIF-4 with ZIF-62.
With 100mA/g current density in the chemical property of the above-mentioned lithium ion half-cell of blue electrical testing system testing, survey
Test result is as shown in table 1.
The battery that be can be seen that from the result shown in table 1 using ZIF-62 as electrode active material not only has excellent head
Secondary charging and discharging capacity, and after 10 charge and discharge cycles, its specific discharge capacity remains within higher value, and becomes
In stabilization, i.e., amplitude of variation is smaller.For example, the specific discharge capacity of the 10th charge and discharge cycles reaches 158mAh/g, fill for the 50th time
The specific discharge capacity of discharge cycles reaches 143.4mAh/g, and the specific discharge capacity of the 100th charge and discharge cycles is even remained able to
Reach 151.1mAh/g.
Also, after tested, after 100 loop tests, ZIF-62 XRD and its XRD basic one before testing
Cause, this explanation ZIF-62 structure in the electrochemical environment of lithium battery will not cave in, therefore be conducive to battery to have good electricity
Chemical stability.
Embodiment 3：
In the present embodiment, the structure of half-cell is substantially the same manner as Example 1, except that negative pole is mixing material, by
Amino ZIF-62, Super-p, PVDF are constituted.
Metal Zn is included in amino ZIF-62 skeleton2+Ion, and imidazoles and aminobenzimidazole, as amino work(
ZIF types of metals organic backbone porous materials can be changed.
Above-mentioned amino ZIF-62 preparation method is as follows：
Presoma containing imidazoles and aminobenzimidazole is C7H7N3With C3H4N2；
Contain Zn2+Soluble-salt be zinc nitrate hexahydrate (Zn (NO3)2·6H2O)；
Organic solvent is N,N-dimethylformamide (DMF)；
15ml DMF are measured in polytetrafluoroethylene (PTFE) pyroreaction kettle, order weighs 0.133g organic compounds C7H7N3、
0.246g C7H7N3With 0.3g zinc nitrate hexahydrates (Zn (NO3)2·6H2O), fall in reactor, add 15ml DMF, make
Uniform with magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover, is put into 130 DEG C of baking oven reactions 72 small
When, obtain reacting coarse product.
The reacting coarse product is washed, washing step is as follows：
(1) reacting coarse product is put into DMF to soak 12 hours, subsequent supersonic oscillations (frequency 40Hz) topple over upper strata muddy
Turbid liquid；
(2) add DMF in surplus solution to soak 12 hours, subsequent supersonic oscillations (frequency 40Hz) topple over upper strata
Turbid solution；
(3) soaking solution, is changed into absolute methanol by this repeat step (2) 2~3 times afterwards, is repeated 2~3 times, is obtained
Reaction product after washing.
Reacting coarse product after washing is put into vacuum drying chamber, 2~3 hours, Ran Housheng are vacuumized under the conditions of 50 DEG C
High-temperature keeps carrying out high-temperature activation in 12 hours to 220 DEG C.Then take out, that is, obtain pure amino functional ZIF types gold
Belong to organic backbone porous material, i.e. amino ZIF-62.
The crystal structure figure that Fig. 3 parses for amino ZIF-62 obtained above single crystal X-ray diffraction result.Fig. 4 is
Minimum repeat unit in crystal structure figure shown in Fig. 3.Fig. 5 is amino ZIF-62 obtained above XRD curves.
As can be seen that the material has ZIF structures, i.e. zeolite imidazole ester skeleton structure from Fig. 3, Fig. 4 and Fig. 5, it is
Porous crystalline material.Contain metal ion, imidazoles and aminobenzimidazole in skeleton, the crosslinking of imidazoles and aminobenzimidazole connects
It is connected on metal, forms a kind of framework of zeolite imidazole esters type.
Amino functional ZIF types of metals organic backbones porous material (hereinafter referred to as MOF materials) obtained above is made
Apply in lithium ion half-cell, comprise the following steps that for electrode material：
(1) by MOF materials obtained above, 80 DEG C of vacuum drying remove what is wherein contained in 12 hours in vacuum drying chamber
Moisture content, is in mass ratio MOF materials：Super-p：PVDF=7：2：1 ratio is mixed with Super-p, PVDF, then adds appropriate
1-METHYLPYRROLIDONE solvent, ball milling 5 hours is well mixed, and obtains slurry；
(2) slurry is coated uniformly on copper foil surface using scraper, cut copper foil after the drying 12 hours of 80 DEG C of vacuum drying oven
Into a diameter of 14cm pole piece, after be put into assembling in the glove box containing inert gas by tabletting, drying, the step such as weighings again
Battery.In the half-cell of assembling, just extremely mixed electrode material, negative pole is lithium piece, and barrier film is Celgard 2400, and electrolyte is
1mol/L lithium hexafluoro phosphates (LiPF6), solvent is that volume ratio is 1：1：1 FEC (fluorinated ethylene carbonate), DMC (carbonic acid diformazans
Ester) with EMC (methyl ethyl carbonate fat) mixed solvent.
With 100mA/g current density in the chemical property of the blue above-mentioned lithium ion battery of electrical testing system testing, test
As a result it is as shown in table 1.
Half-cell using the ZIF-62 of amino functional as electrode active material is can be seen that from the result shown in table 1 not
Only there is excellent first charge-discharge specific capacity, and after 10 charge and discharge cycles, its specific discharge capacity is remained within
Higher value, and tend towards stability, i.e., amplitude of variation is smaller.For example, the specific discharge capacity of the 10th charge and discharge cycles reaches
139.1mAh/g, the specific discharge capacity of the 50th charge and discharge cycles reaches 141.8mAh/g, the electric discharge of the 100th charge and discharge cycles
Specific capacity even remains able to reach 150.8mAh/g.
Also, after 200 loop tests, the XRD of amino functional ZIF types of metals organic backbone porous materials
XRD before being tested with it is basically identical, shown in Figure 6, and this explanation amino functional ZIF types of metals organic backbone is more
Porous materials structure in the electrochemical environment of lithium battery will not cave in, with good electrochemical stability.
Therefore, novel amino functionalization ZIF types of metals organic backbone porous materials obtained above have good electricity
Chemical stability, so as to be had a good application prospect in field of lithium ion battery.
Table 1：MOF materials and circulation specific discharge capacity performance table in embodiment 1-3
Technical scheme is described in detail embodiment described above, it should be understood that it is described above only
For the specific embodiment of the present invention, it is not intended to limit the invention, all any modifications made in the spirit of the present invention,
Supplement or similar fashion replacement etc., should be included in the scope of the protection.
Claims (8)
1. a kind of lithium ion battery electrode material with electrochemical stability, described electrode material includes the organic bone of metal
Frame, it is characterized in that：Comprising at least one ribavirin in described metal organic framework, and at least one metal ion；By N
After secondary charge and discharge cycles, described N is more than or equal to 10, is tested with 100mA/g current density in blue electrical measurement test system,
Its specific discharge capacity circulated every time is higher than 100mAhg-1；
Described ribavirin is the derivative of imidazoles, benzimidazole, aminobenzimidazole, benzimidazole, and amino benzo miaow
Any one in the derivative of azoles；
After n times charge and discharge cycles, since n-th circulation, N is more than or equal to 10, every time the specific discharge capacity base in circulation
Originally more than the 95% of n-th specific discharge capacity is maintained.
2. there is the lithium ion battery electrode material of electrochemical stability as claimed in claim 1, it is characterized in that：Described gold
Belonging to ion includes zinc ion and cobalt ions.
3. there is the lithium ion battery electrode material of electrochemical stability as claimed in claim 1, it is characterized in that：Described gold
Belong to and imidazoles and aminobenzimidazole are included in organic backbone, and configuration metal ions Zn2+Or Co2+。
4. there is the lithium ion battery electrode material of electrochemical stability as claimed in claim 3, it is characterized in that：Described gold
Belonging to the preparation method of organic framework material is：To contain the presoma of imidazoles and aminobenzimidazole as reaction part, with containing
There is Zn2+Soluble-salt or contain Co2+Soluble-salt carry out solvent thermal reaction in organic solvent, obtain ZIF types gold
Belong to organic backbone porous material crude product, it is then that the ZIF types of metals organic backbone porous material crude products is scrubbed, dry
And heating, vacuum activation.
5. there is the lithium ion battery electrode material of electrochemical stability as claimed in claim 4, it is characterized in that：Described contains
The presoma for having imidazoles and aminobenzimidazole includes the simple substance containing imidazoles and aminobenzimidazole, hydrate or metal salt
Compound.
6. there is the lithium ion battery electrode material of electrochemical stability as claimed in claim 4, it is characterized in that：Described contains
There is Zn2+Soluble-salt include zinc nitrate hydrate, zinc acetate hydrate, zinc chloride, one kind in hydrate of zinc sulfata or two
Plant the mixture of the above；Described contains Co2+Soluble-salt include cobalt nitrate hydrate, cobalt acetate hydrate, cobalt chloride, sulphur
Mixture more than one or both of sour cobalt hydrate.
7. the lithium ion battery electrode material with electrochemical stability as described in any claim in claim 1 to 6,
It is characterized in that：After M charge and discharge cycles, described M is more than or equal to 100, described metal-organic framework materials
Structure remains in that intact.
8. a kind of lithium ion battery, it is characterized in that：Its negative electrode material is selected in claim 1 to 6 described in any claim
The lithium ion battery electrode material with electrochemical stability.
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| CN105977483A (en) * | 2016-05-17 | 2016-09-28 | 中国石油大学(华东) | Carbon-based nanocomposite material for electrode |
| CN105836858A (en) * | 2016-06-03 | 2016-08-10 | 华东师范大学 | Method for preparing capacitive desalination electrode |
| KR101930162B1 (en) | 2017-05-26 | 2018-12-17 | 동국대학교 산학협력단 | Sodium-Based Anode Active Material and Secondary Battery Having the Same |
| CN107887603B (en) * | 2017-11-23 | 2020-12-15 | 齐鲁工业大学 | Preparation method of metal organic framework MOF-5 as zinc ion battery positive electrode material |
| CN108807998B (en) * | 2018-05-30 | 2020-11-17 | 武汉理工大学 | Vanadium-based ZIF porous material applied to lithium battery cathode and preparation method thereof |
| KR20210052240A (en) * | 2019-10-31 | 2021-05-10 | 주식회사 엘지화학 | Anode binder for lithium rechargeable battery, anode binder including cured compound of the same anode binder |
| CN111072690A (en) * | 2019-12-25 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | Flower-shaped metal organic framework composite material, and preparation method and application thereof |
| CN113583246A (en) * | 2021-07-22 | 2021-11-02 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method and application of metal organic framework MIL-101-V with three-dimensional mesoporous structure |
| CN114050261B (en) * | 2021-11-04 | 2023-03-31 | 浙江工业大学 | Preparation method of zinc-based battery negative electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102893434A (en) * | 2010-04-21 | 2013-01-23 | 巴斯夫欧洲公司 | Novel metal-organic frameworks as electrode material for lithium ion accumulators |
| CN102921377A (en) * | 2012-06-01 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nitrogen-rich ZMOF type metal-organic framework porous material |
| CN103956502A (en) * | 2014-05-16 | 2014-07-30 | 复旦大学 | Lithium-oxygen battery electrode based on metal organic framework material and preparation method of lithium-oxygen battery electrode |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103230777B (en) * | 2013-05-06 | 2015-07-08 | 北京化工大学 | Large-scale adsorbing material ZIF-8 preparation method and forming method |
-
2014
- 2014-10-14 CN CN201410542330.3A patent/CN104393300B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102893434A (en) * | 2010-04-21 | 2013-01-23 | 巴斯夫欧洲公司 | Novel metal-organic frameworks as electrode material for lithium ion accumulators |
| CN102921377A (en) * | 2012-06-01 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nitrogen-rich ZMOF type metal-organic framework porous material |
| CN103956502A (en) * | 2014-05-16 | 2014-07-30 | 复旦大学 | Lithium-oxygen battery electrode based on metal organic framework material and preparation method of lithium-oxygen battery electrode |
Non-Patent Citations (2)
| Title |
|---|
| "Tunable CO2 Adsorbents by Mixed-Linker Synthesis and Postsynthetic Modification of Zeolitic Imidazolate Frameworks";Joshua A. Thompson等;《The Journal Of Physical Chemistry C》;20130402;第117卷(第16期);第8198～8207页 * |
| "Zeolitic Imidazolate Framework 67-Derived High Symmetric Porous Co3O4 Hollow Dodecahedra with Highly Enhanced Lithium Storage Capability";Renbing Wu等;《Small》;20140225;第10卷(第10期);第1932～1938页 * |
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