CN107808944A - Porous MOF/CNFs composites for lithium anode protection - Google Patents

Porous MOF/CNFs composites for lithium anode protection Download PDF

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CN107808944A
CN107808944A CN201711009439.0A CN201711009439A CN107808944A CN 107808944 A CN107808944 A CN 107808944A CN 201711009439 A CN201711009439 A CN 201711009439A CN 107808944 A CN107808944 A CN 107808944A
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carbon nano
lithium
fiber
metal
porous
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***
孙克宁
王晓东
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Beijing Institute of Technology BIT
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • 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 present invention relates to a kind of porous metal organic frameworks (MOF) and the composite of carbon nano-fiber (CNFs) material composition; protected for lithium anode; can effectively solve the problems, such as lithium anode surface lithium dendrite growth; the cyclical stability of cathode of lithium is improved, improves the battery performance and security of the secondary cell using metal lithium material.

Description

Porous MOF/CNFs composites for lithium anode protection
Technical field
Formed the present invention relates to porous organo-metallic skeleton material (MOF) with carbon nano-fiber (CNFs) material compound Material, protected for lithium anode, belong to field of lithium ion battery.
Background technology
With expanding economy, the portable electric appts such as mobile phone, tablet personal computer, notebook computer have become people's life Indispensable living, and the new tool such as unmanned plane, electrodynamic balance car, electric automobile has also gradually entered into market, leads Industry trend, there is an urgent need to higher energy density, more power density, the more long-life, safer for industry that these are popular Can charge and discharge battery.
Because current economic development is to the heavy dependence of fossil energy and the hysteresis of environmental protection work, Chinese environment Pollution problem is increasingly serious.The large-scale use of fossil energy brings global warming, the EI Nino further triggered Phenomenon starts generally to occur in Chinese scope, and agricultural, fish production activity are produced serious influence.Therefore, people To the extensive using full of expectation of the regenerative resources such as wind energy, solar energy.And wind energy, the utilization ratio of solar energy and local ground Reason situation and weather conditions are closely bound up, and generating efficiency fluctuating range is big, and the electric power quality of production is relatively low, it is difficult to be directly accessed Power network uses.Extensive energy stores converting system has important valency to actual utilize of the regenerative resources such as wind energy, solar energy Value.Therefore, high power capacity, the lithium secondary battery of long-life have huge application prospect in these fields.
Since the 1980s comes out, lithium ion battery is due to higher specific energy, high discharge voltage, circulation Long lifespan, memory-less effect, self-discharge rate are low, operating temperature range is wide and the advantages that safety and environmental protection, are widely used in each Field, especially portable electric appts.The energy density of current commercialized lithium ion battery only has 200~220Wh/kg, By the exploitation of more than ten years, the specific energy and energy density per unit volume of battery are already close to the theoretical energy for being commercialized electrode material Density, room for promotion is very limited, is increasingly difficult to meet the needs of development in science and technology.
Therefore, develop that a kind of specific capacity is high, have extended cycle life, electrode material that security performance is high is particularly important.And metal Lithium has up to 3860mAh/g Theoretical Mass specific capacity, and minimum standard electrode potential, -3.04V (vs.SHE, standard Hydrogen electrode), also with light weight, ductility is good the advantages of, therefore lithium metal is that a kind of have battery material with broad prospects for development Material.But there is problems with lithium metal in actual use：(1) activity of lithium metal is stronger, can occur with electrolyte anti- Should, in the not high SEI films (solid electrolyte interface film) of one layer of intensity of lithium Surface Creation；(2) in the deposition process of lithium, due to Electrode volume changes, and SEI films are more easily damaged, and the fresh lithium being exposed may proceed to and be electrolysed qualitative response, ultimately cause gold Belong to the exhaustion of the irreversible loss and electrolyte of lithium；(3) because the uneven distribution of negative terminal surface lithium ion, metallic lithium surface hold Li dendrite is also easy to produce, can not only destroy SEI films, but also battery diaphragm can be pierced through, causes battery short circuit, produces potential safety hazard. Therefore, commercial applications are not implemented in lithium metal battery so far.
At present, the barrier film generally used in the lithium secondary battery is polyethylene diagrams or polypropylene diaphragm.Due to barrier film The inhomogeneities of pore structure, have impact on uniformity of the lithium ion by barrier film, cause lithium ion on lithium anode surface not Uniform deposition, Li dendrite is produced, barrier film is easily pierced through, brings cell safety problem.
For above mentioned problem existing for lithium anode, researcher has taken up a variety of methods to suppress lithium dendrite growth, Strengthen the stability of negative pole.Li etc. is reacted with polyphosphoric acids (polyphosphoric acid, PPA) and lithium metal, in negative pole table One layer of form compact and stable Li of face in-situ preparation3PO4SEI films.The artificial SEI films of this layer can effectively prevent lithium metal and electrolyte Contact, while there is good mechanical strength, be adapted to Volume Changes of the negative pole in electrode reaction, there is higher lithium Ionic conductivity, effectively inhibit growth (N.W.Li, Y.X.Yin, C.P.Yang, Y.G.Guo, the Adv of Li dendrite Mater,28(2016)1853-1858).Shin etc. coats the nano lamellar graphene (NSG) of S, N doping on barrier film, as Lithium anode protective layer (W.K.Shin, A.G.Kannan, D.W.Kim, ACS Appl Mater Interfaces, 7 (2015)
23700-23707).N in NSG, S hetero atom can strengthen the interaction between lithium anode, reduce Lithium anode surface tension, suppress the growth of Li dendrite, and NSG has good mechanical strength, can prevent Li dendrite Puncture.In addition, NSG can improve the heat endurance of battery diaphragm, the stability of cathode of lithium and barrier film is improved.Liang etc. One layer of polyacrylonitrile (PAN) layers of nanofibers with 3D network structures is placed on cathode of lithium surface, nanofiber surface has Abundant negativity functional group, stronger electrostatic interaction between lithium ion be present so that lithium ion is dispersed, is deposited on network In structure, suppress Li dendrite generation (Z.Liang, G.Zheng, C.Liu, N.Liu, W.Li, K.Yan, H.Yao, P.C.Hsu, S.Chu,Y.Cui,Nano Lett,15(2015)2910-2916)。
Although the above method preferably solves the problems, such as solve lithium anode dendritic growth, there is also some limitations. For example, Li etc. method requires generation Li3PO4Artificial SEI layers need to complete under the atmosphere that anhydrous, anaerobic, argon gas are protected, bar Part is harsher, and production difficulty is big；The cost of graphene used in Shin etc. method is higher, further synthesizes N, S and mixes Miscellaneous NSG further increases the complexity of technique, adds production cost；And 3D network structures in Liang etc. method Polyacrylonitrile (PAN) layers of nanofibers is generated by electrostatic spinning technique, and it has a higher porosity, aperture size compared with Greatly, the dispersion effect of lithium ion is reduced.
Therefore, for problems of the prior art, there is following exploitation demand, more efficiently suppresses lithium branch Brilliant growth, improves the cyclical stability and security of lithium anode, while reduces processing step, reduces production cost.
The content of the invention
Cause it is well known that the lithium dendrite growth on lithium anode surface is mainly negative terminal surface lithium ion skewness 's.Commonly used barrier film is polyethylene diagrams or polypropylene diaphragm in the lithium secondary battery at present, and pore structure is uneven simultaneously And aperture is larger, it can not ensure that lithium ion uniformly reaches negative terminal surface by barrier film, cause lithium ion in lithium anode table The nonuniform deposition in face, Li dendrite is produced, brings cell safety problem.
Reduce while lithium dendrite growth problem the invention aims to efficiently solve lithium anode surface Processing step, reduce production cost.
The invention provides a kind of porous organo-metallic skeleton material/carbon nano-fiber for lithium anode protection (MOF/CNFs) composite, it is prepared by the following method：
(1) bacteria cellulose (BC) aeroge is carbonized under inert gas shielding, the bacterium after being carbonized is fine Dimension element, i.e. carbon nano-fiber (CNFs)；
(2) it is metal-organic framework materials (MOF) and the progress of the carbon nano-fiber of step (1) are compound, obtain porous gold Category-organic framework material/carbon nano-fiber composite material.
In one embodiment of the invention, the MOF materials are unrestricted, as long as it can be in lithium ion battery Keep stable, preferably described MOF has loose structure and is rich in polar group, and more preferably described MOF is selected from HKUST- 1st, the one or more in MIL-53, Cu-Co-ZIF, ZIF-8, ZIF-9 or ZIF-67, most preferably ZIF-8.
In one embodiment of the invention, bacteria cellulose (BC) aeroge is by bacterial fibers BC hydrogels Obtained by being freeze-dried.It is highly preferred that cleaning and soaking BC hydrogel with water, then freeze-drying obtains BC aeroges.
In one embodiment of the invention, using solution synthetic method, hydro-thermal method, infusion process or Mechanical Method by MOF with CNFs carries out compound.Preferably, make MOF and CNFs progress compound using solution reaction, CNFs is dispersed in MOF precursor In solution, MOF synthesis is then carried out, MOF is supported on CNFs, you can to obtain porous MOF/CNFs composites.It is preferred that Ground, CNFs are evenly spread in MOF precursor solution before MOF synthesis or when synthesis starts, and dispersing mode is unrestricted, excellent Gated ultrasonic disperse.Preferably, MOF metal precursor solutions and organic ligand precursor solution are prepared respectively, CNFs is uniform Be dispersed at least one of metal precursor solutions and organic ligand precursor solution solution, subsequent hybrid metal precursor solution and Organic ligand precursor solution synthesizes MOF.
In one embodiment of the invention, MOF and CNFs weight ratio can be adjusted suitably, preferred weight ratio For 3:1 to 1:1.
Invention further provides a kind of lithium ion battery separator, and porous MOF/CNFs composites are mixed with binding agent Uniform slurry is synthesized, the surface coated in lithium ion battery separator, forms porous MOF/CNFs composite coatings.
In one embodiment of the invention, wherein, the thickness of lithium ion battery separator coating can be adjusted suitably Section, preferably 10~50 microns.
In one embodiment of the invention, wherein, porous MOF/CNFs composites can be fitted with binding agent Work as regulation, preferred weight ratio 9：1 to 8:2, more preferably 9:1.
Invention further provides application of the porous MOF/CNFs composites in lithium ion battery, wherein, it is porous MOF/CNFs composites are between lithium ion battery separator and lithium anode.It is more according to one embodiment of the present invention Hole MOF/CNFs composites can be coated in lithium ion battery separator surface, lithium anode surface or independent protection is made Film.
The porous MOF/CNFs composites of the present invention are used to protect lithium anode and lithium ion battery separator, more increase Effect ground suppresses the growth of Li dendrite, improves the cyclical stability and security of lithium anode, while has that technique is simple, raw material The features such as cost is low, it is adapted to industrial applications.Specifically, the present invention has advantages below：
(1) CNFs is generated by bacteria cellulose by simple carbonisation, and bacteria cellulose comes from agricultural product and added The byproduct of industrial and commercial bank's industry, material source is wide, cheap, is also beneficial to improve the utilization rate of resource.CNFs is as composite Skeleton, there is three-dimensional space network structure and good electric conductivity.Porous network structure contributes to the dispersed of lithium ion, And good electric conductivity can reduce electrode local current densities, delay the growth of Li dendrite；
(2) MOF is supported on CNFs surfaces by simple in-situ synthetic method, and MOF materials have huge specific surface area And nano-porous structure, mesoporous, microcellular structure compared to CNFs, MOF nano-pore structure can preferably disperse lithium ion.And And the negative group that MOF material surfaces enrich also plays important function to the dispersed of lithium ion；
(3) porous MOF/CNFs composites have good chemical stability, can be made into slurry with industrial class binding agent Material, is coated in membrane surface by the tape casting, is more suitable for commercial process.
Brief description of the drawings
Carbon nano-fiber SEM shape appearance figures after Fig. 1 BC aeroges carbonizations of the present invention；
Fig. 2 carbon nano-fibers of the present invention in methyl alcohol disperse after SEM shape appearance figures；
Fig. 3 the present invention porous ZIF-8/CNFs composites SEM shape appearance figures, wherein in upper figure ZIF-8 and CNF weight Amount is than being 3:1, ZIF-8 and CNF weight ratio is 1 in figure below:1；
The graph of pore diameter distribution of the porous ZIF-8/CNFs composites of Fig. 4 present invention；
The organigram of the lithium ion battery of the porous MOF/CNFs composite coatings of Fig. 5 application present invention, wherein, 1 is lithium anode, and 2 be porous MOF/CNFs composite coatings, and 3 be barrier film, and 4 be electrolyte, and 5 be positive pole.
Fig. 6 is using leaching of the lithium ion battery separator of the porous ZIF-8/CNFs composite coatings of the present invention to electrolyte Lubricant nature energy, wherein, (a) is the barrier films of Celgard 2400, and contact angle is 81 °, and (b) is the porous ZIF-8/CNFs of the application present invention The lithium ion battery separator of composite coating, contact angle are 42 °.
Fig. 7 is put using the lithium ion battery separator of the porous ZIF-8/CNFs composite coatings of the present invention at the 10th time The SEM shape appearance figures of lithium anode after electricity, (a) use Celgard2400 barrier films；(b) using the porous ZIF-8/ of the present invention CNFs composite coating modified diaphragms.
Fig. 8 uses the Li/LiCoO of ZIF-8/CNFs composite coatings modified diaphragm of the present invention2Cycle charge-discharge it is bent Line.
Embodiment
For present disclosure, substantive features and marked improvement is expanded on further, following examples detailed description is hereby enumerated It is as follows, but the present invention is not limited to following examples.
Embodiment 1
1) bacteria cellulose (BC) hydrogel is cut into suitable fritter first, is cleaned with deionized water and soak 24h, so Afterwards BC aeroges are obtained by freeze-drying.Afterwards, BC aeroges are carbonized (2h) in the case where 900 DEG C of argon gas protect atmosphere, Obtain be carbonized bacteria cellulose, i.e. carbon nano-fiber (CNFs).
2) 3mmol zinc nitrate hexahydrate is dissolved in 30mL methanol, 100mg carbon nano-fibers is then added, in the bar of ice bath Ultrasonic 20min under part, fully dispersed carbon nano-fiber.Afterwards, 12mmol methylimidazole is dissolved in 10mL methanol, then added Enter in the first solution, slight stirring, ensure that two kinds of solution are sufficiently mixed, stand 24h.Finally, carry out centrifuge washing and (use methanol Cleaning), the removal of impurity is gone, sediment drying can obtain to ZIF-8 and CNFs composite.During this, it can properly increase Methylimidazole promotes the ratio of zinc nitrate hexahydrate the progress of reaction.ZIF-8 and CNFs ratio can also be changed to adjust Section load capacity (such as ZIF-8 and CNFs weight ratio is 1:1).
Fig. 1 shows the carbon nano-fiber SEM shape appearance figures after the carbonization of BC aeroges, and Fig. 2 shows carbon nano-fiber in first SEM shape appearance figures after disperseing in alcohol, Fig. 3 show the SEM shape appearance figures of the porous ZIF-8/CNFs composites of the present invention.
The specific surface area of the porous ZIF-8/CNFs composites of the present invention is 1034.51m2g-1, it has nanoporous Structure, pore-size distribution are as shown in Figure 4.
When the porous MOF/CNFs composites of the present invention are used as into lithium ion battery separator modified coating, CNFs effectively drops Low cathode of lithium surface local current densities, slow down the growth of Li dendrite, meanwhile, CNFs three-dimensional network loose structure and The huge specific surface area of MOF materials and nano-porous structure, ensure that uniformity of the lithium ion by barrier film, so as to improve lithium from Uniformity of the son in lithium anode surface distributed, it is suppressed that the generation of Li dendrite.
Embodiment 2
By the porous ZIF-8/CNFs composites of the present invention and adhesive according to weight than 9:1 blendes together uniform slurry, Coated in lithium ion battery separator surface, certain thickness modified coating is formed.It can be answered by adjusting porous ZIF-8/CNFs The thickness of the ratio and coating of condensation material and binding agent further adjusts the performance of coating, such as the thickness of coating can control System is at 10~50 μm.
Then, the lithium ion battery separator with porous ZIF-8/CNFs composite coatings is applied in lithium ion battery In, the structure of battery is as shown in Figure 5.Lithium ion battery plus-negative plate contains electrode reaction active material, and it is anti-that electrolyte provides battery The passage for answering ion to transmit, Celgard2400 membranes apart battery plus-negative plates, prevents battery short circuit.It is more in battery assembling Hole ZIF-8/CNFs composite modification coatings are in contact with lithium anode.Porous MOF/CNFs composite modifications coating makes Obtain lithium ion to be uniformly distributed in negative terminal surface, stable metal cathode of lithium.
It is coating modified to lithium ion battery separator progress by using the porous ZIF-8/CNFs composites of the present invention, can It is as shown in table 1 below to significantly change the characteristic of lithium-ion membrane.As seen from Table 1, porous ZIF-8/CNFs composite modifications Although coating brings the reduction by a small margin of porosity, but considerably increase the pick up of barrier film, reduces ion diffusion resistance, So as to improve ionic conductivity.
Table 1
Fig. 6 show the present invention porous ZIF-8/CNFs composite coatings improve electrolyte to lithium ion battery every The wellability of film.
Using copper foil as positive pole, lithium piece as negative pole, barrier film be respectively adopted Celgard2400 and the present invention it is porous ZIF-8/CNFs composite coating modified diaphragms, form Cu/Li batteries.Charging and discharging currents density is 0.5mA cm-2, the 10th After secondary electric discharge, battery is peeled off in glove box, the surface topography of lithium anode surface lithium deposition is observed under ESEM, As shown in Figure 7.It can be seen that modified barrier film can cause lithium ion in lithium anode surface uniform deposition, effectively to suppress Grow Li dendrite, strengthen the cyclical stability of lithium anode.Table 2 has been further listed in using different materials protection cathode of lithium Cu/Li batteries 120 circle circulation after average coulombic efficiencies.The porous ZIF-8/CNFs composite coatings of the present invention are low Higher coulombic efficiency is shown under current density and high current density, it was demonstrated that MOF/CNFs composites of the present invention can be with Lithium dendrite growth is restrained effectively, improves the cyclical stability of cathode of lithium.
Table 2
Embodiment 3
Using commercially produced product cobalt acid lithium pole piece as positive pole, lithium piece uses ZIF-8/CNFs of the present invention as negative pole, barrier film Composite coating modified diaphragm, composition battery carry out charge-discharge test under 0.5C multiplying powers, as a result as shown in Figure 8.It can see Go out, using the Li/LiCoO of ZIF-8/CNFs composite coatings modified diaphragm of the present invention2Battery shows good circulation Stability, after 100 circles are circulated under 0.5C, specific capacity remains at 110mAh g-1More than, average coulombic efficiency is more than 98%. This test result further proves that the MOF/CNFs composites of the present invention can improve the cyclical stability of lithium anode.
Applicant states that the present invention illustrates the detailed process of the present invention, but not office of the invention by above-described embodiment It is limited to foregoing description, that is, does not mean that the present invention has to rely on foregoing detailed description and could implemented.The technology of art Personnel it will be clearly understood that any improvement in the present invention, the addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, Selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims (12)

1. porous organo-metallic skeleton material/carbon nano-fiber (MOF/CNFs) composite protected for lithium anode, It is prepared by the following method：
(1) bacteria cellulose aeroge is carbonized under inert gas shielding, the bacteria cellulose after being carbonized, i.e. carbon Nanofiber；
(2) metal-organic framework materials and the carbon nano-fiber of step (1) are carried out to compound, acquisition porous organo-metallic skeleton Material/carbon nano-fiber composite material.
2. porous organo-metallic skeleton material/carbon nano-fiber composite material as claimed in claim 1, wherein, the gold The one kind or more of category-organic framework material in HKUST-1, MIL-53, Cu-Co-ZIF, ZIF-8, ZIF-9 or ZIF-67 Kind.
3. porous organo-metallic skeleton material/carbon nano-fiber composite material as claimed in claim 1 or 2, wherein, it is described Bacteria cellulose aeroge is to be obtained by bacteria cellulose aquagel by being freeze-dried.
4. porous organo-metallic skeleton material/carbon nano-fiber composite material as described in claim any one of 1-3, wherein, Using solution synthetic method, hydro-thermal method, infusion process or Mechanical Method by the carbon nano-fiber of metal-organic framework materials and step (1) Carry out compound.
5. porous organo-metallic skeleton material/carbon nano-fiber composite material as claimed in claim 4, wherein, using solution Metal-organic framework materials and the carbon nano-fiber of step (1) are carried out compound, the carbon nanometer that step (1) is obtained by reaction method Fiber is dispersed in the precursor solution of metal-organic framework materials, then carries out the synthesis of metal-organic framework materials, Metal-organic framework materials are made to be supported on carbon nano-fiber, you can to obtain porous organo-metallic skeleton material/carbon Nanowire Tie up composite.
6. porous organo-metallic skeleton material/carbon nano-fiber composite material as claimed in claim 5, wherein, step (2) The metal precursor solutions and organic ligand precursor solution of middle preparing metal-organic framework material respectively, carbon nano-fiber is uniform Be dispersed at least one of metal precursor solutions and organic ligand precursor solution solution, subsequent hybrid metal precursor solution and Organic ligand precursor solution synthesizes metal-organic framework materials.
7. porous organo-metallic skeleton material/carbon nano-fiber composite material as described in claim any one of 1-6, wherein, The weight of metal-organic framework materials and carbon nano-fiber ratio is 3:1 to 1:1.
8. a kind of lithium ion battery separator, porous organo-metallic skeleton material/carbon described in claim any one of 1-7 is received Rice fibrous composite is mixed into uniform slurry with binding agent, the surface coated in lithium ion battery separator, forms porous gold Category-organic framework material/carbon nano-fiber composite material coating.
9. lithium ion battery separator as claimed in claim 8, wherein, the thickness of coating is 10~50 microns.
10. lithium ion battery separator as claimed in claim 8 or 9, wherein, porous organo-metallic skeleton material/carbon Nanowire The weight ratio for tieing up composite and binding agent is 9:1 to 8:2.
11. porous organo-metallic skeleton material/carbon nano-fiber composite material described in claim any one of 1-7 lithium from Application in sub- battery, wherein, porous organo-metallic skeleton material/carbon nano-fiber composite material is in lithium ion battery separator Between lithium anode.
12. porous organo-metallic skeleton material/carbon nano-fiber composite material as claimed in claim 11 is in lithium ion battery In application, wherein, porous organo-metallic skeleton material/carbon nano-fiber composite material is coated in lithium ion battery separator table Independent diaphragm is made in face, lithium anode surface.
CN201711009439.0A 2017-10-25 2017-10-25 Porous MOF/CNFs composites for lithium anode protection Pending CN107808944A (en)

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CN108428841A (en) * 2018-03-26 2018-08-21 中国科学院青岛生物能源与过程研究所 A kind of cellulose nanometer fibril/metal organic frame composite lithium ion cell diaphragm and preparation method
CN108649173A (en) * 2018-05-31 2018-10-12 湖北大学 A kind of porous septum and its with the integrated preparation method of metal negative electrode and purposes
CN108976818A (en) * 2018-07-02 2018-12-11 华南理工大学 The porous orderly carbon-point of one kind is based on cellulose composite material and the preparation method and application thereof
CN109216048A (en) * 2018-08-14 2019-01-15 南京理工大学 Flexible electrode and preparation method thereof based on bacteria cellulose film
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CN111403692A (en) * 2020-03-09 2020-07-10 重庆天齐锂业有限责任公司 Preparation method of metal lithium cathode with hydrophobic protective layer
CN112216817A (en) * 2019-07-12 2021-01-12 华为技术有限公司 Metal negative electrode, preparation method thereof and secondary battery
CN112750983A (en) * 2020-12-31 2021-05-04 合肥国轩高科动力能源有限公司 Three-dimensional composite lithium metal negative electrode, preparation method thereof and lithium battery
CN112750986A (en) * 2020-12-31 2021-05-04 华东理工大学 Metallic lithium cathode with high-ionic-conductivity artificial SEI film and preparation method thereof
CN112952033A (en) * 2021-03-03 2021-06-11 珠海冠宇动力电池有限公司 Pole piece and battery
CN114006131A (en) * 2020-07-28 2022-02-01 宁德时代新能源科技股份有限公司 Diaphragm, electronic device comprising diaphragm and preparation method of electronic device
CN114583174A (en) * 2022-03-21 2022-06-03 蜂巢能源科技股份有限公司 Sodium ion battery and preparation method thereof
CN114824228A (en) * 2022-05-16 2022-07-29 西南科技大学 Lithium ion battery cathode material and preparation method thereof

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CN108428841A (en) * 2018-03-26 2018-08-21 中国科学院青岛生物能源与过程研究所 A kind of cellulose nanometer fibril/metal organic frame composite lithium ion cell diaphragm and preparation method
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CN108976818A (en) * 2018-07-02 2018-12-11 华南理工大学 The porous orderly carbon-point of one kind is based on cellulose composite material and the preparation method and application thereof
CN109216048A (en) * 2018-08-14 2019-01-15 南京理工大学 Flexible electrode and preparation method thereof based on bacteria cellulose film
CN109216048B (en) * 2018-08-14 2020-04-21 南京理工大学 Flexible electrode based on bacterial cellulose membrane and preparation method thereof
WO2021008467A1 (en) * 2019-07-12 2021-01-21 华为技术有限公司 Metal negative electrode, preparation method therefor, and secondary battery
CN112216817A (en) * 2019-07-12 2021-01-12 华为技术有限公司 Metal negative electrode, preparation method thereof and secondary battery
CN110600739A (en) * 2019-08-22 2019-12-20 浙江工业大学 Preparation method of metal lithium negative electrode protection layer material
CN111081995A (en) * 2019-11-07 2020-04-28 东北大学 Preparation method of metal oxide carbon nanofiber electrode material based on MOFs derivation
CN111282522A (en) * 2020-02-10 2020-06-16 四川大学 Metal organic framework composite aerogel material and preparation method and application thereof
CN111403692B (en) * 2020-03-09 2023-01-20 重庆天齐锂业有限责任公司 Preparation method of metal lithium cathode with hydrophobic protective layer
CN111403692A (en) * 2020-03-09 2020-07-10 重庆天齐锂业有限责任公司 Preparation method of metal lithium cathode with hydrophobic protective layer
CN114006131A (en) * 2020-07-28 2022-02-01 宁德时代新能源科技股份有限公司 Diaphragm, electronic device comprising diaphragm and preparation method of electronic device
WO2022021591A1 (en) * 2020-07-28 2022-02-03 宁德时代新能源科技股份有限公司 Diaphragm, electrical apparatus comprising diaphragm, and production method therefor
CN112750983A (en) * 2020-12-31 2021-05-04 合肥国轩高科动力能源有限公司 Three-dimensional composite lithium metal negative electrode, preparation method thereof and lithium battery
CN112750986A (en) * 2020-12-31 2021-05-04 华东理工大学 Metallic lithium cathode with high-ionic-conductivity artificial SEI film and preparation method thereof
CN112750986B (en) * 2020-12-31 2023-05-26 华东理工大学 Metallic lithium negative electrode with high-ionic-conductivity artificial SEI film and preparation method thereof
CN112952033A (en) * 2021-03-03 2021-06-11 珠海冠宇动力电池有限公司 Pole piece and battery
CN114583174A (en) * 2022-03-21 2022-06-03 蜂巢能源科技股份有限公司 Sodium ion battery and preparation method thereof
CN114583174B (en) * 2022-03-21 2024-03-26 蜂巢能源科技股份有限公司 Sodium ion battery and preparation method thereof
CN114824228A (en) * 2022-05-16 2022-07-29 西南科技大学 Lithium ion battery cathode material and preparation method thereof
CN114824228B (en) * 2022-05-16 2023-06-16 西南科技大学 Lithium ion battery negative electrode material and preparation method thereof

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Application publication date: 20180316