CN109980235A - A kind of metal secondary batteries cathode preparation method and application of low volume variation - Google Patents
A kind of metal secondary batteries cathode preparation method and application of low volume variation Download PDFInfo
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- CN109980235A CN109980235A CN201910277909.4A CN201910277909A CN109980235A CN 109980235 A CN109980235 A CN 109980235A CN 201910277909 A CN201910277909 A CN 201910277909A CN 109980235 A CN109980235 A CN 109980235A
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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
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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
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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
- H01M10/42—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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of composite three-dimensional porous collector of spinning film and its preparation method and application is provided, the composite three-dimensional porous collector of spinning film includes three-dimensional porous current collector material and the spinning film formed by electrostatic spinning technique for being covered on its surface, and the spinning film is solid electrolyte interface film.High face amount metal deposit, dendrite inhibition growth may be implemented in the collector, and alleviates electrode volume variation, to improve the safety and cycle life of metal negative electrode.
Description
Technical field
The invention belongs to electrochemical energy storage fields, and in particular to a kind of three-dimensional porous collector of hydridization, preparation method,
It is secondary using the safety of the cathode, long-service-life metal using the high security metal negative electrode of the three-dimensional porous collector of the hydridization
Battery and its application in high-energy density type energy storage device.
Background technique
With becoming increasingly conspicuous for conventional fossil fuel burning bring problem of environmental pollution, there is an urgent need to develop go out more by people
For clean energy system.Due to having many advantages, such as high energy density and excellent cyclical stability, lithium ion battery is in hand
The small consumers energy field such as machine, laptop and robot is widely applied.Current commercialized lithium ion battery
In, it is the lithium ion battery of anode and assembling using graphite as cathode, ternary material, energy density can achieve about 180Wh
kg-1, can be for electric automobile during traveling 300km or so.In order to meet, electric car, energy storage power grid and space equipment etc. are high-power to be set
Standby demand needs one kind of exploitation higher energy density directly using the secondary cell of the metal negative electrodes such as lithium, sodium, potassium and magnesium.
By taking lithium metal secondary battery as an example, because of the advantages that lithium metal voltage is low, density is small and specific capacity is high, the secondary cell of assembling
Theoretical energy density be 2-3 times of commercial Li-ion batteries, there is important Development volue and application prospect.
The study found that the critical issue of lithium metal battery future application is to solve the safety issue of cathode.Lithium metal is straight
It connects as cathode, because of the nonuniform deposition of lithium metal, Li dendrite can be generated in electrochemistry cyclic process repeatedly.Li dendrite
Further growth can pierce through diaphragm, cause internal short-circuit of battery, so as to cause inside battery fever even it is on fire.Li dendrite
Formation also results in biggish electrode volume variation, reduces the safety and cycle life of battery.
In order to solve the problems, such as Li dendrite, one of effective solution method is consolidating between modified metal lithium and electrolyte
Body electrolyte interface film (SEI film).In artificial SEI film (such as patent of lithium metal or copper current collector surface construction
CN108649173A, CN108649232A etc.) it can be reacted to avoid the fast-growth and lithium metal and electrolyte contacts of dendrite,
And then improve lithium metal deposit-coulombic efficiency is precipitated.But since lithium metal is a kind of no acceptor material and copper foil storage lithium space
It is limited, therefore, in charge and discharge process, lithium anode there are biggish volume change, so as to cause entire battery occur compared with
Big volume expansion and contraction, brings serious safety issue.Three-dimensional collector, because of specific surface area with higher and hole
Hold, can accommodate higher face amount lithium and alleviate cyclic process in volume change (such as patent CN107785586A,
CN104716330A etc.).But since the SEI film of its conductive characteristic and surface be not able to maintain stabilization in long circulating process,
Li dendrite is inevitably formed on its surface and grows.The present invention is the dendritic growth and electricity solved in metal secondary batteries
Polar body accumulates variation issue, proposes to construct the compound metal negative electrode that a kind of integrated three-dimensional collector and artificial SEI film are integrated.Benefit
Metal is accommodated with the big memory space of three-dimensional porous collector, ion stream can not only be sieved by reaching using the SEI film on surface, but also can
To prevent dendrite from growing on collection liquid surface, to guarantee that entire cathode maintains electrode volume to stablize in charge and discharge process.
The operating procedure is simple, safely and effectively, can be mass-produced.
Summary of the invention
Technical problem solved by the invention is to provide a kind of hydridization as metal secondary batteries negative current collector
Three-dimensional porous collector, the collector are to integrate the spinning film that three-dimensional porous collector and artificial SEI spinning film are integrated to answer
Close three-dimensional porous collector.Compared to using plate collector (such as copper foil or metal negative electrode itself), or simple three-dimensional porous collection
Fluent material (nickel foam, foam copper, foamed aluminium, titanium foam, porous carbon, graphene, carbon nanotube, three-dimensional carbon material etc.), or
The collector of other modes coating process, the application show to obtain by the technology of electrostatic spinning specific in porous three-dimensional collector
The spinning film of structure, can not only may be implemented high face amount metal deposit, dendrite inhibition growth, and more importantly can be with
Alleviate electrode volume variation, to improve the safety and cycle life of metal negative electrode.In addition, preparing the spinning film complex three-dimensional
Porous current collector it is easy to operate, it is at low cost, can large-scale production, have very high practicability.
Specifically, the composite three-dimensional porous collector of spinning film provided by the present application, it is characterised in that: including three-dimensional porous
Current collector material and the spinning film formed by electrostatic spinning technique for being covered on its surface, the spinning film are solid electrolyte
Interfacial film.
3-50 μm of thickness of the spinning film, it is 0.001-0.02cm that perforations per unit area, which holds,3/cm2, aperture 50-
1000nm, preferred thickness are 5-30 μm, and it is 0.002-0.01cm that perforations per unit area, which holds,3/cm2, aperture 100-500nm.In practice
It was found that the thickness of comprehensively control spinning film, perforations per unit area hold and this several, aperture parameter, it can be in battery cathode preparation process
In, so that lithium ion enters the duct of porous current collector quickly through the spinning film, meanwhile, it can also be better protected from duct
The formation of Li dendrite, and prevent the volume expansion of cathode of lithium in charge and discharge process.
Wherein the three-dimensional current collector material is selected from following at least one: nickel foam, foam copper, foamed aluminium, titanium foam, bubble
Foam carbon, porous carbon, graphene, carbon nanotube, three-dimensional carbon material, preferred three-dimensional carbon material.
Wherein the solid electrolyte interface film (SEI film) is by being selected from inorganic oxide (such as silica, aluminium oxide and oxygen
Change titanium etc.), inorganic ions conductor (such as Li3PO4, LiTi2(PO4)3, LiGe2(PO4)3, Li7La3Zr2O12, Li4SiO4, Li4GeO4
Deng), one of inorganic porous material (such as metal organic frame MOF, covalent organic frame COF, zeolite-imidazoles frame ZIF)
Or different materials are combined with polymer.It is preferred that by metal organic frame MOF, covalent organic frame COF or zeolite-miaow
Azoles frame ZIF is combined with polymer.
The polymer is at least selected from following at least one: PEO, PVDF, PAN, PMMA, PLA etc., preferably PVDF, PAN and
PMMA。
The present invention also provides a kind of preparation methods of composite three-dimensional porous afflux of spinning film, wherein is included in three-dimensional porous
The surface of current collector material forms spinning film by the means of electrostatic spinning.Preferably, the composite three-dimensional porous collection of spinning film
Fluid is made of three-dimensional carbon fiber and the spinning film that is covered on it, the spinning film by metal organic frame powder with polymerize
The slurries that object is prepared, then electrostatic spinning forms a film again, dries and obtains.
For example, the preparation method of the composite three-dimensional porous collector of spinning film, comprising the following steps:
(1), under argon atmosphere protection, commercialized cotton is placed in carbide furnace, 900-1400 DEG C of high temperature cabonization
1-20h, obtained three-dimensional carbon fiber；
(2), according to a certain percentage (1:9-8:1) by the powder of MOF (such as MOF808) this high-modulus and polymer
Uniformly mixing, it is stand-by to be prepared into slurries；
(3), the three-dimensional carbon fiber being carbonized by cotton is laid on copper foil, the slurries prepared is injected into spinning and are set
In standby syringe, setting operation voltage is 5-25kV, and the reception distance between the needle point of spinning equipment and three-dimensional carbon fiber is
5-25cm, the flow velocity of injection are 0.1-2mL/h；The spinning film is formed by the technology of electrostatic spinning, after dry, the three-dimensional
Spinning film on carbon fiber with a thickness of 3-50 μm, it is 0.001-0.02cm that perforations per unit area, which holds,3/cm2, aperture 50-
1000nm。
It is preferred that above-mentioned spinning film takes out after dry in 70-90 DEG C of vacuum drying 5-20h and is used for battery testing.It is preferred that control
Preparing high-temp carburizing temperature is 1000-1200 DEG C, and the high temperature cabonization time is 4-6h, is formed by three-dimensional carbon fiber and is conducive to subsequent spinning
The formation of cortina and the control of spinning film properties
The ratio of the metal organic frame powder and polymer is 1:9-8:1, preferably 1:1-6:1；
The condition of the technology of the electrostatic spinning is that operation voltage is 5-25kV, preferably 10-20kV, more preferable 10-
12kV；Reception distance between the needle point and three-dimensional carbon fiber is 5-25cm, preferably 10-20cm, more preferable 15-17cm.
The flow velocity of the injection is 0.1-2mL/h, preferably 0.2-1mL/h, preferably 0.5-1mL/h.
It is preferred that control the spinning film with a thickness of 5-30 μm, it is 0.002-0.01cm that perforations per unit area, which holds,3/cm2, aperture
For 100-500nm.
The spinning film is the fibre structure for the class bead string type being compounded to form by MOF-808 particle and polymer.
Application provided by the present invention is the composite three-dimensional porous collector of spinning film as metal secondary batteries negative pole currect collecting
The application of body, the metal secondary batteries, which refer to, directly uses the two of one of lithium metal, sodium, potassium and magnesium or a variety of effect cathode
Primary cell, the composite three-dimensional porous collector of spinning film is to integrate three-dimensional porous current collector material and solid polymer electrolytic
The collector that plasma membrane is integrated.
In addition, the present invention also provides preparing high security, long-life, high energy using the metal secondary batteries of above-mentioned cathode
Application in metric density type energy storage device.
It is compared to the method for commonly preparing interface coating, such as physical blending coating method (such as patent
CN108649173A), slurry is easy filling three-dimensional space, blocks the duct of three-dimensional material, is only applicable to plate collector (such as copper
Foil) surface coating, the electrostatic spinning technique, may be implemented plate even three-dimensional porous collection liquid surface uniform coating.
In addition, being flexible material as three-dimensional carbon fiber especially for three-dimensional porous material, it is easier to using the technology of coating
The duct of three-dimensional material is blocked, the application uses quiet by rationally controlling the preparation process condition of three-dimensional carbon fibre material
The technology of Electrospun forms the spinning film of particular bore appearance, aperture and thickness in three-dimensional carbon fiber surface, reduces duct blocking
Meanwhile the volume expansion of battery cathode is effectively prevented, also inhibit the formation of Li dendrite.
Detailed description of the invention
Fig. 1 is the scanning electron microscope cross-section photograph that the HCF of MOF spinning film is compounded in embodiment 1.
Fig. 2 is the scanning electron microscope planar picture that the HCF of MOF spinning film is compounded in embodiment 1.
Fig. 3 is the HCF deposition 6mA h cm that MOF spinning film is compounded in embodiment 1-2The cathode scanning electron of lithium metal is aobvious
Micro mirror cross-section photograph.
Fig. 4 is that the HCF of MOF spinning film is compounded in embodiment 1, is assembled into Li | Li Symmetrical cells are in current density
1mA cm-2, capacity is 1mA h cm-2Under the conditions of cyclical stability test.
Fig. 5 is the HCF that MOF spinning film is compounded in embodiment 1, is assembled into full battery, in the case where current density is 0.2C
Long circulating performance test.
Fig. 6 is the HCF deposition 15mA h cm that MOF spinning film is compounded in embodiment 2-2The cathode scanning electron of lithium metal
Microscope cross-section photograph.
Fig. 7 is the scanning electron microscope cross-section photograph that the graphene of MOF coating is coated in comparative example 2.
Fig. 8 is the graphene deposition 8mA h cm that MOF coating is coated in comparative example 3-2The cathode of lithium metal.
Fig. 9 is the scanning electron microscope cross-section photograph that the carbon nanotube of MOF coating is coated in comparative example 3.
Figure 10 is the carbon nanotube deposition 8mA h cm that MOF coating is coated in comparative example 4-2The cathode of lithium metal.
Figure 11 is the scanning electron microscope cross-section photograph that the carbon nano-fiber of MOF coating is coated in comparative example 4.
Figure 12 is the carbon nano-fiber deposition 8mA h cm that MOF coating is coated in comparative example 5-2The cathode of lithium metal.
Figure 13 is to deposit 8mA h cm in comparative example 5 by collector of blank copper foil-2The cathode scanning electron of lithium metal is aobvious
Micro mirror cross-section photograph.
Figure 14 is to be assembled into Li using blank copper foil as collector in comparative example 5 | Li Symmetrical cells are 1mA in current density
cm-2, capacity is 1mA h cm-2Under the conditions of cyclical stability test.
Figure 15 is to be assembled into full battery using blank copper foil as collector in comparative example 5, the length in the case where current density is 0.2C
Cycle performance test.
Figure 16 is to deposit 8mA h cm by collector of the copper foil that MOF is modified in comparative example 6-2The cathode of lithium metal scans electricity
Sub- microscope cross-section photograph.
Figure 17 is to be assembled into Li using the copper foil of MOF modification as collector in comparative example 6 | Li Symmetrical cells, in current density
For 1mA cm-2, capacity is 1mA h cm-2Under the conditions of cyclical stability test.
Figure 18 is to be assembled into full battery using the copper foil of MOF modification as collector in comparative example 6, is 0.2C in current density
Under long circulating performance test.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the present invention is not limited to following embodiments.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
(1) the composite three-dimensional porous collector of spinning film is prepared: firstly, under argon atmosphere protection, by commercialized cotton
It is placed on inside carbide furnace, the three-dimensional carbon fiber that 1200 DEG C of high temperature cabonization 4h are obtained.Secondly, MOF-808 powder is pressed with PVDF
It is mixed according to 3:1 ratio uniform, it is stand-by to be prepared into slurries.Then, the three-dimensional carbon fiber being carbonized by cotton is laid in completely
Copper foil on, the slurries prepared are injected into 10mL syringe, setting operation voltage is 10kV, needle point and three-dimensional carbon fiber it
Between reception distance be 10cm, the flow velocity of injection is 0.5mL/h；Film is formed by the technology of electrostatic spinning, it is then true at 80 DEG C
The dry 10h of sky, forms the composite three-dimensional porous collector of spinning film, takes out and be used for battery testing after dry.The spinning film
With a thickness of 17 μm, it is 0.003cm that perforations per unit area, which holds,3/cm2, aperture is the spinning film of 100-500nm, and the spinning film is compound
The overall thickness of three-dimensional porous collector is about 122 μm, and electron microscope cross-section photograph is as shown in Figure 1.Wherein, the spinning film tool
There is the fibre structure for the class bead string type being compounded to form by MOF-808 particle and polymer, as shown in Figure 2.
(2) with the more empty set fluid preparation three-dimensional combination electrodes of spinning film complex three-dimensional obtained in step (1)
It regard the composite three-dimensional porous collector of spinning film (i.e. MOF-HCF) as cathode, lithium piece is anode, by electrochemistry side
Method lithium deposition 6mA h cm-2。
It can be seen that under the protective effect of spinning film from Fig. 3 scanning electron microscope cross-section photograph, lithium metal uniformly sinks
Product is inside three-dimensional porous carbon fiber, and surface does not have dendroid Li dendrite, the thickness of the three-dimensional combination electrode after deposited metal lithium
It is about 119 μm of degree, close with the composite three-dimensional porous afflux body thickness of spinning film before deposition, volume change is only-
2.5%.
(3) with above-mentioned three-dimensional combination electrode assembling half-cell and its performance test
By above-mentioned three-dimensional combination electrode (i.e. MOF-HCF) as anode, lithium metal is assembled as cathode and electrolyte to obtain the final product
Lithium metal secondary battery.
Constant current charge-discharge test is carried out to above-mentioned battery using charge and discharge instrument, test capacity cutoff is 1mA h cm-2, test
Temperature is 25 DEG C.Fig. 4 is the cathode of lithium in 1mA cm-2Cyclical stability under current density.It can be seen that in circulation 1100
Voltage still keeps stable after hour, and voltage polarizing very little.
(4) lithium metal secondary battery electro-chemical test
Three-dimensional combination electrode (MOF-HCF@Li) and any appropriate positive (phosphoric acid prepared by above-mentioned electrochemical deposition method
Iron lithium anode LFP), electrolyte assembles up to lithium metal secondary battery.The face amount of iron phosphate lithium positive pole is 2-3mA h cm-2,
Test blanking voltage is 2-4V, and test temperature is 25 DEG C, and test current density is 0.2-1.0C.Fig. 5 shows MOF-HCF@Li |
The reversible capacity of LFP battery can achieve 160mA hg-1, 200 circles, capacity retention ratio 91.3% are recycled, cubical expansivity is
2.7%.
Embodiment 2
Other conditions are same as Example 1, the difference is that (one) passes through electrochemical method lithium deposition 15mAh cm-2。
Fig. 6 shows, for lithium metal uniform deposition inside three-dimensional porous carbon fiber, surface does not have a dendroid Li dendrite, deposited metal lithium it
The thickness of three-dimensional combination electrode afterwards is about 124 μm, close with the thickness of electrode before deposition, and electrode volume change rate is only-
1.6%.The cathode of lithium is in 1mA cm-2It can be recycled under current density 700 hours.The MOF-HCF@Li of assembling | LFP battery
Reversible capacity can achieve 161mA h g-1, 200 circle of circulation, capacity retention ratio 91.8%, cubical expansivity 2.1%.
Embodiment 3
Other conditions are same as Example 1, the difference is that 1000 DEG C of high temperature cabonizations.The spinning film with a thickness of 15
μm, it is 0.002cm that perforations per unit area, which holds,3/cm2, aperture is the spinning film of 100-500nm, the composite three-dimensional porous collection of spinning film
The overall thickness of fluid is about 111 μm.By electrochemical method lithium deposition 6mA h cm-2, lithium metal uniform deposition is three-dimensional porous
Inside carbon fiber, surface does not have dendroid Li dendrite, and the thickness of the three-dimensional combination electrode after deposited metal lithium is about 115 μm,
Close with the thickness of electrode before deposition, electrode volume change rate is only -3.6%.The cathode of lithium is in 1mA cm-2Current density
Under can recycle 800 hours.The MOF-HCF@Li of assembling | the reversible capacity of LFP battery can achieve 158mA h g-1, circulation
200 circles, capacity retention ratio 90%, cubical expansivity 4.0%.
Embodiment 4
Other conditions are same as Example 1, the difference is that 1500 DEG C of high temperature cabonizations.The spinning film with a thickness of 10
μm, it is 0.02cm that perforations per unit area, which holds,3/cm2, aperture is the spinning film of 300-800nm, the composite three-dimensional porous collection of spinning film
The overall thickness of fluid is about 96 μm.By electrochemical method lithium deposition 6mA h cm-2, lithium metal is largely deposited on three-dimensional porous
Inside carbon fiber, but since the aperture on surface is larger, part metals lithium can deposit to surface by aperture, deposited metal lithium it
The thickness of three-dimensional combination electrode afterwards is about 101 μm, and electrode volume change rate is -5.2%.The cathode of lithium is in 1mA cm-2Electricity
It can be recycled under current density 600 hours.The MOF-HCF@Li of assembling | the reversible capacity of LFP battery can achieve 150mA hg-1,
200 circle of circulation, capacity retention ratio 86%, cubical expansivity 8%.
Embodiment 5
Other conditions are same as Example 1, the difference is that operation voltage is 20kV.The spinning film with a thickness of 13
μm, it is -0.006cm that perforations per unit area, which holds,3/cm2, aperture is the spinning film of 300-500nm, and the spinning film is composite three-dimensional porous
The overall thickness of collector is about 106 μm.By electrochemical method lithium deposition 6mA h cm-2, lithium metal uniform deposition is more in three-dimensional
Inside the carbon fiber of hole, surface does not have dendroid Li dendrite, and the thickness of the three-dimensional combination electrode after deposited metal lithium is about 110 μ
Thickness of electrode before m, with deposition is close, and electrode volume change rate is only -3.8%.The cathode of lithium is in 1mA cm-2Electric current is close
It can be recycled 850 hours under degree.The MOF-HCF@Li of assembling | the reversible capacity of LFP battery can achieve 159mA h g-1, circulation
200 circles, capacity retention ratio 91%, cubical expansivity 4.5%.
Embodiment 6
Other conditions are same as Example 1, the difference is that operation voltage is 20kV.The spinning film with a thickness of 12
μm, it is 0.001cm that perforations per unit area, which holds,3/cm2, aperture is the spinning film of 100-200nm, the composite three-dimensional porous collection of spinning film
The overall thickness of fluid is about 95 μm.By electrochemical method lithium deposition 6mAh cm-2, since perforations per unit area appearance and aperture are smaller,
The transmission of lithium ion is obstructed, and lithium metal is presented non-uniform deposition, and part metals lithium deposits to surface, after deposited metal lithium
The thickness of three-dimensional combination electrode is about 102 μm, and electrode volume change rate is only -7.3%.The cathode of lithium is in 1mA cm-2Electric current
It can be recycled under density 520 hours.The MOF-HCF@Li of assembling | the reversible capacity of LFP battery can achieve 146mA h g-1, follow
Ring 200 encloses, capacity retention ratio 85%, cubical expansivity 8%.
Embodiment 7
Other conditions are same as Example 1, the difference is that the flow velocity of injection is 1mL/h.The thickness of the spinning film
It is 16 μm, it is 0.003cm that perforations per unit area, which holds,3/cm2, aperture is the spinning film of 400-500nm, and the spinning film complex three-dimensional is more
The overall thickness of hole collector is about 115 μm.By electrochemical method lithium deposition 6mA h cm-2, lithium metal uniform deposition is in three-dimensional
Inside porous carbon fiber, surface does not have dendroid Li dendrite, and the thickness of the three-dimensional combination electrode after deposited metal lithium is about 119
μm, close with the thickness of electrode before deposition, electrode volume change rate is only -3.5%.The cathode of lithium is in 1mA cm-2Electric current
It can be recycled under density 880 hours.The MOF-HCF@Li of assembling | the reversible capacity of LFP battery can achieve 160mA h g-1, follow
Ring 200 encloses, capacity retention ratio 90.8%, cubical expansivity 4.1%.
Embodiment 8
Other conditions are same as Example 1, the difference is that the flow velocity of injection is 0.1mL/h.The thickness of the spinning film
Degree is 21 μm, and it is 0.001cm that perforations per unit area, which holds,3/cm2, aperture is the spinning film of 50-100nm, the spinning film complex three-dimensional
The overall thickness of porous current collector is about 118 μm.By electrochemical method lithium deposition 6mA h cm-2, due to perforations per unit area hold and
Aperture is smaller, and the transmission of lithium ion is obstructed, and non-uniform deposition is presented in lithium metal, and part metals lithium deposits to surface, deposition gold
The thickness for belonging to the three-dimensional combination electrode after lithium is about 124 μm, and electrode volume change rate is -5.1%.The cathode of lithium is in 1mA
cm-2It can be recycled under current density 595 hours.The MOF-HCF@Li of assembling | the reversible capacity of LFP battery can achieve 145mA
h g-1, 200 circle of circulation, capacity retention ratio 87%, cubical expansivity 7%.
Embodiment 9
Other conditions are same as Example 1, the difference is that the flow velocity of injection is 2mL/h.The thickness of the spinning film
It is 24 μm, it is 0.001cm that perforations per unit area, which holds,3/cm2, aperture is the spinning film of 50-200nm, and the spinning film complex three-dimensional is more
The overall thickness of hole collector is about 126 μm.By electrochemical method lithium deposition 6mA h cm-2, since flow velocity is very fast, the non-shape of coating
It at class bead string type structure, is mainly formed by MOF particle, and due to the traction action of not no fiber, many MOF particles are direct
It is filled into the three-dimensional porous fibrous inside in bottom, blocks fibroplastic duct.Since no enough ducts accommodate lithium metal, gold
Belong to lithium and can up grow until lithium metal pierces through surface covering, subsequent lithium is induced to form dendroid Li dendrite, deposited metal lithium it
The thickness of three-dimensional combination electrode afterwards is about 133 μm, and electrode volume change rate is only -5.6%.The cathode of lithium is in 1mA cm-2
It can be recycled under current density 550 hours.The MOF-HCF@Li of assembling | the reversible capacity of LFP battery can achieve 147mA h
g-1, 200 circle of circulation, capacity retention ratio 86%, cubical expansivity 9%.
Embodiment 10
Other conditions are same as Example 1, the difference is that (one) is equal according to 1:9 ratio by MOF-808 powder and PEO
Even mixing, electrostatic spinning operation voltage are set as 20kV, and the reception distance between needle point and the three-dimensional porous afflux of hydridization is
20cm, the flow velocity of injection are 1mL/h；By the technology of electrostatic spinning, spinning on a layer thickness in three-dimensional collection liquid surface is 25 μm,
It is 0.005cm that perforations per unit area, which holds,3/cm2, aperture is the coating of 500-800nm, and electrode overall thickness is about 130 μm.Wherein, due to
MOF-808 particle fraction is less, and the class bead string type structure that coating is shown is less, the fibre structure mainly formed by PEO spinning.
Since the fiber mechanical modulus that PEO spinning is formed is lower, part metals lithium pierces through surface covering, and subsequent lithium is induced to form dendroid
The thickness of Li dendrite, the three-dimensional combination electrode after deposited metal lithium is big compared with the thickness of electrode before deposition, electrode volume expansion
Rate is -10%.
Embodiment 11
Other conditions are same as Example 1, the difference is that (one) will be by MOF-808 powder and PLA according to 5:1 ratio
Uniformly mixing, electrostatic spinning operation voltage are set as 5kV, and the reception distance between needle point and the three-dimensional porous afflux of hydridization is
5cm, the flow velocity of injection are 1.5mL/h；By the technology of electrostatic spinning, spinning on a layer thickness in three-dimensional collection liquid surface is 15 μ
M, it is 0.007cm that perforations per unit area, which holds,3/cm2, aperture is the coating of 700-900nm, and electrode overall thickness is about 131 μm.Wherein, by
More in MOF-808 particle fraction, the operation voltage of setting is lower, and reception is closer, and flow velocity is very fast, the not formed class pearl of coating
String data structure is mainly formed by MOF particle, and due to the traction action of not no fiber, many MOF particles are directly filled into
The three-dimensional porous fibrous inside in bottom, blocks fibroplastic duct.Since no enough ducts accommodate lithium metal, lithium metal meeting
Up growth is until lithium metal pierces through surface covering, and subsequent lithium is induced to form dendroid Li dendrite, and three after deposited metal lithium
The thickness for tieing up combination electrode is big compared with the thickness of electrode before deposition, and electrode volume expansion rate is -10%.
Embodiment 12
Other conditions are same as Example 1, the difference is that (one) will be by MOF-808 powder and PMMA according to 6:1 ratio
Example uniformly mixing, electrostatic spinning operation voltage are set as 15kV, the reception distance between needle point and the three-dimensional porous afflux of hydridization
For 15cm, the flow velocity of injection is 0.3mL/h；By the technology of electrostatic spinning, spinning on a layer thickness in three-dimensional collection liquid surface is
20 μm, it is 0.005cm that perforations per unit area, which holds,3/cm2, aperture is the coating of 200-300nm, and electrode overall thickness is about 130 μm.Its
In, coating is the fibre structure for the class bead string type being compounded to form by MOF-808 particle and polymer.The fiber that spinning is formed is mechanical
Modulus is higher, and for lithium metal uniform deposition inside three-dimensional porous carbon fiber, surface does not have a dendroid Li dendrite, deposited metal lithium it
The thickness of three-dimensional combination electrode afterwards and the thickness of electrode before deposition approach, and electrode volume expansion rate is only -2.6%.It is described
Cathode of lithium is in 1mA cm-2It can be recycled under current density 750 hours.The MOF-HCF@Li of assembling | the reversible capacity of LFP battery can
To reach 157mA h g-1, 200 circle of circulation, capacity retention ratio 92%, cubical expansivity 4.3%.
Embodiment 13
Other conditions are same as Example 1, the difference is that (one) lithium anode collector, selects foam copper foil to make
For collector.Than more loose inside foam copper foil, there are biggish holes, can accommodate a certain amount of lithium metal.By electrification
Method lithium deposition 8mA h cm-2.Lithium metal is deposited on the inner space of foam copper foil formation, and surface does not have dendroid lithium branch
Crystalline substance, electrode material still maintain presedimentary thickness, and electrode volume expansion rate is only -3.1%.
Embodiment 14
Other conditions are same as Example 1, the difference is that (one) lithium anode collector, selects foam nickel foil to make
For collector.Than more loose inside foam nickel foil, there are biggish holes, can accommodate a certain amount of lithium metal.By electrification
Method lithium deposition 8mA h cm-2.Lithium metal is deposited on the inner space of foam nickel foil formation, and surface does not have dendroid lithium branch
Crystalline substance, electrode material still maintain presedimentary thickness, and electrode volume expansion rate is only -3.6%.
Comparative example 1
Other conditions are same as Example 1, the difference is that the method that (one) prepares interface coating, selects physical blending
Coating method, rather than electrostatic spinning technique.MOF-808 powder is mixed with PVDF according to 3:1 ratio uniform, is coated in by cotton
On the three-dimensional carbon fiber that flower carbonization obtains.Since the inside of carbon nano-fiber is than more loose, there are certain hole, and MOF
Grain is smaller, after physics coats, penetrates into inside carbon nano-fiber, is filled with a part of hole, reduces lithium metal appearance
The amount received.Since no enough ducts accommodate lithium metal, lithium metal can up be grown until lithium metal puncture surface covering, lures
It leads subsequent lithium and forms dendroid Li dendrite, the thickness of the three-dimensional combination electrode after deposited metal lithium is thick compared with the electrode before deposition
Degree is big, and electrode volume expansion rate is -16%.
Comparative example 2
Other conditions are same as Example 1, the difference is that (one) lithium anode collector, is selected graphene coated
Copper foil as collector, then by MOF and PVDF according to 3:1 ratio, be uniformly mixed, then, the method coated using physics
It is coated in the copper foil surface of graphene modified.From fig. 6, it can be seen that existing certain than more loose inside graphene coated copper foil
Hole, and MOF particle is smaller, after physics coats, penetrates into inside graphene, is filled with a part of hole, reduces
The amount that lithium metal accommodates.By electrochemical method lithium deposition 8mA h cm-2.Fig. 7 shows that lithium metal is raw along copper foil bottom end
Inner space long, that filled graphite alkene is formed, with the increase of deposition, lithium metal can grow into surface layer, become dendrite, simultaneously
Electrode volume is caused to expand.
Comparative example 3
Other conditions are same as Example 1, the difference is that (one) lithium anode collector, selects carbon coating nanometer
Then MOF and PVDF is uniformly mixed by the copper foil of pipe as collector according to 3:1 ratio, then, the side coated using physics
Method is coated in carbon nano tube modified copper foil surface.From figure 8, it is seen that depositing inside the copper foil of carbon nano-tube coating than more loose
In certain hole, and MOF particle is smaller, after physics coats, penetrates into inside carbon nanotube, is filled with a part of hole
Gap reduces the amount of lithium metal receiving.By electrochemical method lithium deposition 8mA h cm-2.Fig. 9 shows that lithium metal is along copper foil
Bottom end growth, the inner space that filling carbon nano-pipe is formed, with the increase of deposition, lithium metal can grow into surface layer, become
Dendrite also results in electrode volume expansion.
Comparative example 4
Other conditions are same as Example 1, the difference is that (one) lithium anode collector, selects carbon coating nanometer
Then MOF and PVDF is uniformly mixed by the copper foil of fiber as collector according to 3:1 ratio, then, using physics coating
Method is coated in the copper foil surface of carbon nano-fiber modification.From fig. 10 it can be seen that comparing inside the copper foil of coating carbon nano-fiber
Loose, there are certain holes, and MOF particle is smaller, after physics coats, penetrates into inside carbon nano-fiber, filling
A part of hole reduces the amount of lithium metal receiving.By electrochemical method lithium deposition 8mA h cm-2.Figure 11 shows, metal
Lithium is grown along copper foil bottom end, and the inner space that filling carbon nano-fiber is formed, with the increase of deposition, lithium metal can be grown
To surface layer, become dendrite, also results in electrode volume expansion.
Comparative example 5
Other conditions are same as Example 1, the difference is that (one) lithium anode collector, selects blank copper foil to make
For collector.By electrochemical method lithium deposition 8mA h cm-2.It can be seen that from Figure 12 scanning electron microscope cross-section photograph
Tube-like condition is presented in lithium metal, is apparent dendrite behavior, it is micro- that the thickness of the electrode after deposited metal lithium increases about 98
Rice, electrode volume expansion rate reach -392%.Figure 13 is the cathode of lithium in 1mA cm-2Cyclical stability under current density.
It can be seen that voltage increases after circulation 150 hours, polarization becomes larger, and Symmetrical cells voltage-time curve shows bottle-neck song
Line.Figure 14 shows Cu@Li | the reversible capacity of LFP electrode is 138mA h g-1, 200 circle of circulation, capacity retention ratio 78%.Figure
15 displays are assembled into full battery using blank copper foil as collector, the long circulating performance test in the case where current density is 0.2C.
Comparative example 6
Other conditions are same as Example 1, the difference is that (one) lithium anode collector, selects MOF physics to apply
The copper foil of modification is covered as collector.By electrochemical method lithium deposition 8mA h cm-2To obtain the final product.From Figure 16 scanning electron microscope
Cross-section photograph can be seen that lithium metal and be stored between copper foil and MOF layers in fine and close form, and sandwich structure is presented.Due to
The space that copper surface does not accommodate, lithium metal can only deposit on its surface, cause thickness of electrode obvious after deposited metal lithium
Increase.The thickness of electrode after deposited metal lithium increases about 51 microns, and electrode volume expansion rate reaches -110%.Figure 17
It is the cathode of lithium in 1mAcm-2Cyclical stability under current density.It can be seen that voltage increases after circulation 700 hours, pole
Change becomes larger.Figure 17 shows MOF-Cu@Li | the reversible capacity of LFP electrode is 142mA h g-1, 200 circles are recycled, capacity retention ratio is
87%.Figure 18 is shown using the copper foil of MOF modification as collector, is assembled into full battery, the long circulating in the case where current density is 0.2C
Performance test.
Claims (10)
1. a kind of composite three-dimensional porous collector of spinning film, it is characterised in that: including three-dimensional porous current collector material and be covered on
The spinning film formed by electrostatic spinning technique on its surface, the spinning film are solid electrolyte interface film.
2. three-dimensional porous collector described in claim 1, wherein 3-50 μm of thickness of the spinning film, perforations per unit area hold
For 0.001-0.02cm3/cm2, aperture 50-1000nm, preferred thickness is 5-30 μm, and it is 0.002- that perforations per unit area, which holds,
0.01cm3/cm2, aperture 100-500nm.
3. the described in any item three-dimensional porous collectors of claim 1-2, wherein it is described three-dimensional current collector material be selected from it is following extremely
Few one kind: nickel foam, foam copper, foamed aluminium, titanium foam, foamy carbon, porous carbon, graphene, carbon nanotube, three-dimensional carbon material,
Preferred three-dimensional carbon material.
4. the described in any item three-dimensional porous collectors of claim 1-4, wherein the solid electrolyte interface film (SEI film)
By being selected from inorganic oxide (such as silica, aluminium oxide and titanium oxide), inorganic ions conductor (such as Li3PO4, LiTi2
(PO4)3, LiGe2(PO4)3, Li7La3Zr2O12, Li4SiO4, Li4GeO4Deng), inorganic porous material (such as metal organic frame MOF,
Covalent organic frame COF, zeolite-imidazoles frame ZIF) one of or different materials and polymer be combined；It is preferred that by
Metal organic frame MOF, covalent organic frame COF or zeolite-imidazoles frame ZIF and polymer are combined；
The polymer is at least selected from following at least one: PEO, PVDF, PAN, PMMA, PLA, preferably PVDF, PAN and PMMA.
5. a kind of preparation method of the composite three-dimensional porous afflux of spinning film, wherein including the table in three-dimensional porous current collector material
Face forms spinning film by the means of electrostatic spinning.
6. preparation method described in claim 5, wherein the composite three-dimensional porous collector of spinning film by three-dimensional carbon fiber and
The spinning film composition being covered on it, the slurries that the spinning film is obtained by metal organic frame powder and polymer formulation,
Then electrostatic spinning forms a film again, dries and obtains.
7. preparation method as claimed in claim 6, comprising the following steps:
(1), under argon atmosphere protection, commercialized cotton is placed in carbide furnace, 900-1400 DEG C of high temperature cabonization 1-
20h, obtained three-dimensional carbon fiber；
(2), the powder of MOF (such as MOF808) this high-modulus and polymer is uniform according to a certain percentage (1:9-8:1)
Mixing, it is stand-by to be prepared into slurries；
(3), the three-dimensional carbon fiber being carbonized by cotton is laid on copper foil, the slurries prepared is injected into spinning equipment
In syringe, setting operation voltage is 5-25kV, and the reception distance between the needle point of spinning equipment and three-dimensional carbon fiber is 5-
25cm, the flow velocity of injection are 0.1-2mL/h；The spinning film is formed by the technology of electrostatic spinning, after dry, the three-dimensional carbon
Spinning film on fiber with a thickness of 3-50 μm, it is 0.001-0.02cm that perforations per unit area, which holds,3/cm2, aperture 50-1000nm.
8. preparation method as claimed in claim 7, wherein control high temperature cabonization temperature is 1000-1200 DEG C, the high temperature cabonization time
For 4-6h.
9. preparation method according to any one of claims 8, wherein the operation voltage is 10-20kV, more preferable 10-12kV；The needle
Reception distance between point and three-dimensional carbon fiber is 10-20cm, more preferable 15-17cm；The flow velocity of the injection is 0.2-1mL/
H, preferably 0.5-1mL/h；Control the spinning film with a thickness of 5-30 μm, it is 0.002-0.01cm that perforations per unit area, which holds,3/
cm2, aperture 100-500nm.
10. any one of the composite three-dimensional porous collector of any one of the claim 1-4 spinning film or claim 5-9 system
Application of the composite three-dimensional porous collector of spinning film that Preparation Method is prepared as metal secondary batteries negative current collector.
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| CN110581310A (en) * | 2019-10-09 | 2019-12-17 | 电子科技大学 | method for inhibiting growth of lithium dendrite by coating organic compound |
| CN111952543A (en) * | 2020-08-24 | 2020-11-17 | 广东工业大学 | Three-dimensional lithium metal electrode, preparation method thereof and lithium metal battery |
| CN112259714A (en) * | 2020-09-29 | 2021-01-22 | 东莞东阳光科研发有限公司 | Solid-state battery composite electrode plate, preparation method thereof and solid-state battery comprising solid-state battery composite electrode plate |
| CN112349911A (en) * | 2020-07-27 | 2021-02-09 | 上海恩力动力技术有限公司 | Porous metal current collector, preparation method, negative electrode and battery |
| CN112490410A (en) * | 2020-11-26 | 2021-03-12 | 宁波大学 | PEO-TiO for inhibiting growth of lithium dendrite2Composite film material and preparation method thereof |
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| CN111952543A (en) * | 2020-08-24 | 2020-11-17 | 广东工业大学 | Three-dimensional lithium metal electrode, preparation method thereof and lithium metal battery |
| CN112259714A (en) * | 2020-09-29 | 2021-01-22 | 东莞东阳光科研发有限公司 | Solid-state battery composite electrode plate, preparation method thereof and solid-state battery comprising solid-state battery composite electrode plate |
| CN114930572A (en) * | 2020-11-10 | 2022-08-19 | 株式会社Lg新能源 | Negative electrode for all-solid battery and all-solid battery including the same |
| CN112490410A (en) * | 2020-11-26 | 2021-03-12 | 宁波大学 | PEO-TiO for inhibiting growth of lithium dendrite2Composite film material and preparation method thereof |
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| CN114068872A (en) * | 2021-10-13 | 2022-02-18 | 江苏恒力化纤股份有限公司 | Polymer nanofiber metal lithium composite negative electrode with double lithium affinity and preparation method thereof |
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