CN105609783B - A kind of carbon structure collector, battery cathode, anode and lithium battery - Google Patents
A kind of carbon structure collector, battery cathode, anode and lithium battery Download PDFInfo
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- CN105609783B CN105609783B CN201610195413.9A CN201610195413A CN105609783B CN 105609783 B CN105609783 B CN 105609783B CN 201610195413 A CN201610195413 A CN 201610195413A CN 105609783 B CN105609783 B CN 105609783B
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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
- H01M4/663—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
- 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
- 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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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention provides a kind of carbon structure collector, including：Foamy graphite；It is attached to the alumina layer on the foamy graphite surface；It is attached to the carbon nanotubes on the alumina layer surface.The present invention provides a kind of battery cathode, including：Carbon structure collector described in above-mentioned technical proposal；It is attached to the lithium metal of the carbon structure collection liquid surface.The present invention provides a kind of anodes, are prepared as the carbon structure collector described in above-mentioned technical proposal.The present invention provides a kind of lithium battery, including the battery cathode and/or anode described in above-mentioned technical proposal.Carbon structure collector provided by the invention is preferentially filled up the hole of collector, avoids point effect during lithium metal planar growth using three-dimensional carbon material, lithium metal along carbon cannon born frame deposition growing.Therefore, carbon collector provided by the invention can effectively inhibit the growth of metal Li dendrite, so that lithium battery has preferable cyclicity and security, also have higher energy density.
Description
Technical field
The present invention relates to electrochemical power source technical field more particularly to a kind of carbon structure collector, battery cathode, battery just
Pole and lithium battery.
Background technology
In recent years, with the development of mobile electron electric appliance and wearable device, lithium battery is widely used.But
In current lithium battery, what battery cathode was generally selected is graphite, and the theoretical specific capacity of graphite only has 372mAh g-1, energy
Metric density is low, it is difficult to meet the needs of today's society, there is an urgent need to a kind of batteries of high-energy density to carry out meet demand by people.And
Lithium metal has high capacity density, and (theoretical specific capacity is 3860mAh g-1) and minimum potential (- 3.040V vs. standards
Hydrogen electrode).But lithium metal be used as battery cathode when, since current density and lithium ion are unevenly distributed in charge and discharge process
Factor, lithium ion form dendrite in negative terminal surface nonuniform deposition.Dendritic growth can not only pierce through membrane, cause battery short circuit,
And battery can consume electrolyte repeatedly in cyclic process, reduce the utilization rate of cathode, so as to cause lithium ion battery
Poor circulation, security performance are low.
The content of the invention
In view of this, it is an object of the invention to provide a kind of carbon structure collector, battery cathode, anode and lithium electricity
Pond, the lithium battery that carbon structure collector provided by the invention, battery cathode or anode are prepared have preferable cycle
Performance and security, and energy density is higher.
The present invention provides a kind of carbon structure collector, including：
Foamy graphite；
It is attached to the alumina layer on the foamy graphite surface；
It is attached to the carbon nanotubes on the alumina layer surface.
Preferably, the density of the foamy graphite is 3mg cm-3~50mg cm-3。
Preferably, the thickness of the foamy graphite is 1.7mm~1.9mm.
Preferably, the hole of the foamy graphite is 400 μm~500 μm.
Preferably, a diameter of 10nm~30nm of the carbon nanotubes.
Preferably, the mass ratio of the carbon nanotubes and foamy graphite is (2~4)：1.
Preferably, the pore volume of the carbon structure collector is 0.8cm3g-1~1.1cm3g-1；
The specific surface area of the carbon structure collector is 230m2g-1~270m2g-1。
Carbon structure collector provided by the invention uses three-dimensional carbon material, and lithium metal is excellent along carbon cannon born frame deposition growing
The hole of collector is first filled up, avoids point effect during lithium metal planar growth.Therefore, carbon collector provided by the invention
The growth of metal Li dendrite can effectively be inhibited.
The present invention provides a kind of battery cathode, including：
Carbon structure collector described in above-mentioned technical proposal；
The lithium metal being attached on the carbon structure collector.
The present invention provides a kind of anode, including the carbon structure collector described in above-mentioned technical proposal.
In the present invention, the carbon structure collector has porous structure, and this porous structure can be used in carried metal
Lithium prepares anode, can inhibit the growth of metal Li dendrite, and lithium battery is made to have preferable cyclicity and security.
The present invention provides a kind of lithium battery, including the battery cathode described in above-mentioned technical proposal and/or above-mentioned technical side
Anode described in case.
Lithium battery provided by the invention is safe, long lifespan, also has higher energy density.
Description of the drawings
It in order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention, for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the picture for the foamy graphite that the embodiment of the present invention 1 is prepared；
Fig. 2 is the picture for the carbon structure collector that the embodiment of the present invention 2 is prepared；
Fig. 3 is the picture for the battery cathode that the embodiment of the present invention 3 is prepared；
Fig. 4 is the constant current charge-discharge curve for the battery that the embodiment of the present invention 4 is prepared；
Fig. 5 is scanning electron microscope (SEM) picture after the Symmetrical cells Xun Huan that the embodiment of the present invention 4 is prepared；
Fig. 6 is scanning electron microscope (SEM) picture after the Symmetrical cells Xun Huan that the embodiment of the present invention 5 is prepared；
Fig. 7 is the first charge-discharge curve for the lithium-sulfur cell that the embodiment of the present invention 7 is prepared；
Fig. 8 is the cycle-index-specific discharge capacity curve for the lithium-sulfur cell that the embodiment of the present invention 7 is prepared.
Specific embodiment
The technical solution in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiments obtained without making creative work belong to the model that the present invention protects
It encloses.
The present invention provides a kind of carbon structure collector, including：
Foamy graphite；
It is attached to the alumina layer on the foamy graphite surface；
It is attached to the carbon nanotubes on the alumina layer surface.
Carbon structure collector provided by the invention includes foamy graphite.In the present invention, the density of the foamy graphite is excellent
Elect 3mg cm as-3~50mg cm-3, more preferably 10mg cm-3~40mg cm-3, it is most preferably 20mg cm-3~30mg cm-3.In the present invention, the thickness of the foamy graphite is preferably 1.7mm~1.9mm, more preferably 1.75mm~1.85mm, optimal
Elect 1.8mm as.In the present invention, the hole of the foamy graphite is preferably 400 μm~500 μm, more preferably 420 μm~480 μ
m；More preferably 440 μm~460 μm, be most preferably 450 μm.
In the present invention, the preparation method of the foamy graphite is preferably：
Graphene is grown using chemical vapour deposition technique on foam metal surface, obtains graphene template；
The graphene template is dissolved or is electrolysed, obtains foamy graphite.
In the present invention, the foam metal is preferably porous foam metal.In the present invention, the foam metal is preferred
For nickel foam or foam copper.In the present invention, the pore-size distribution of the foam metal is preferably 100ppi~120ppi, more preferably
It is most preferably 110ppi for 105ppi~115ppi.In the present invention, the surface density of the foam metal is preferably 30mg m-2
~50mg m-2, more preferably 35mg m-2~45mg m-2, it is most preferably 40mg m-2。
The present invention does not have special limitation to the specific method of chemical vapour deposition technique growth graphene, using ability
The technical solution of process for preparing graphenes by chemical vapour deposition known to field technique personnel carries out chemical vapor deposition with hydrocarbon
Product.In the present invention, the growth temperature of the chemical vapour deposition technique growth graphene is preferably 1000 DEG C~1100 DEG C,
More preferably 1020 DEG C~1080 DEG C, be most preferably 1040 DEG C~1060 DEG C.In the present invention, the chemical vapour deposition technique life
The growth time of long graphene is preferably 5 minutes~90 minutes, more preferably 20 minutes~70 minutes, most preferably 40 minutes~
50 minutes.
In the present invention, the detailed process of the chemical vapour deposition technique growth graphene is：
Hydrocarbon postcooling is passed through into foam metal, grows graphene on foam metal surface.
In the present invention, the hydrocarbon is preferably methane or ethylene.In the present invention, the hydrocarbon
Flow is preferably 40sccm~60sccm, more preferably 45sccm~55sccm, is most preferably 50sccm.In the present invention, institute
The time that is passed through for stating hydrocarbon is preferably 3 minutes~7 minutes, more preferably 5 minutes.The present invention is preferably in the atmosphere of Ar
Carry out above-mentioned cooling.In the present invention, the flow of the Ar is preferably 400sccm~600sccm, and more preferably 450sccm~
550sccm is most preferably 500sccm.In the present invention, the speed of the cooling is preferably 5 DEG C/min~15 DEG C/min, more excellent
It elects 8 DEG C/min~12 DEG C/min as, is most preferably 10 DEG C/min.
In the present invention, it is excellent before hydrocarbon is passed through into foam metal to anneal to foam metal.In this hair
In bright, preferably in Ar and H2Mixed airflow under carry out the annealing.In the present invention, the flow of Ar is excellent in the annealing process
It elects 300sccm~500sccm as, more preferably 350sccm~450sccm, is most preferably 400sccm.In the present invention, it is described
H in annealing process2Flow be preferably 40sccm~60sccm, more preferably 45sccm~55sccm, be most preferably 50sccm.
In the present invention, the temperature of the annealing is preferably 1000 DEG C~1100 DEG C, more preferably 1020 DEG C~1080 DEG C, is most preferably
1050℃.In the present invention, the time of the annealing is preferably 20 minutes~40 minutes, more preferably 25 minutes~35 minutes,
Most preferably 30 minutes.
In the present invention, the graphene template is dissolved or is electrolysed, to remove the gold of the foam in graphene template
Belong to.In the present invention, the solvent of the dissolving is preferably hydrochloric acid, nitric acid or iron chloride.In the present invention, the electrolysis of the electrolysis
Liquid is preferably the electrolyte containing nickel salt.In the present invention, the nickel salt is preferably nickel chloride.In the present invention, the nickel salt
Concentration in the electrolytic solution is preferably 0.5mol/L~1.5mol/L, more preferably 0.8mol/L~1.2mol/L, is most preferably
1mol/L.In the present invention, the voltage of the electrolysis is preferably 2V~2.5V, more preferably 2.2V.In the present invention, the electricity
The time of solution is preferably 8 minutes~12 minutes, more preferably 10 minutes.
In the present invention, it is dry after obtained electrolysate is washed after the completion of the electrolysis, obtain foamy graphite.
In the present invention, the reagent of the washing is preferably water and ethyl alcohol.In the present invention, the water is preferably deionized water.In this hair
In bright, the temperature of the drying is preferably 40 DEG C~60 DEG C, more preferably 45 DEG C~55 DEG C, is most preferably 50 DEG C.
Carbon structure collector provided by the invention includes the alumina layer for being attached to the foamy graphite surface.In the present invention
In, the thickness of the alumina layer is preferably 1nm~10nm, more preferably 2nm~8nm, is most preferably 3nm~6nm.In this hair
In bright, the preparation method of the alumina layer is：
In foamy graphite surface deposited catalyst, catalyst layer is formed；
In the catalyst layer surface using atomic layer deposition method deposition of aluminium oxide, alumina layer is formed.
In the present invention, the method for deposited catalyst be preferably magnetron sputtering method, electron-beam vapor deposition method, thermal evaporation or from
Sub- sputtering method, more preferably magnetron sputtering method.In the present invention, the catalyst is preferably iron, cobalt or nickel, more preferably iron.
In the present invention, the deposition thickness of the catalyst is preferably 3nm~5nm, more preferably 4nm.In the present invention, it is preferred to it is steeping
Foam graphite surface deposits Fe using magnetron sputtering method, forms catalyst layer.In the present invention, the pressure of magnetron sputtering Fe is preferably
3Pa~6Pa, more preferably 4Pa~5Pa.In the present invention, the electric current of magnetron sputtering Fe is preferably 10mA~20mA, more preferably
It is most preferably 14mA~15mA for 12mA~18mA.In the present invention, the sedimentation time of magnetron sputtering Fe be preferably 280s~
320s, more preferably 300s.
In the present invention, use the specific method of atomic layer deposition method deposition of aluminium oxide for：
In atomic layer deposition apparatus, aluminium organic matter will be contained and reacted with foamy graphite, obtain reaction product；
The reaction product with water is reacted, foamy graphite surface is made to grow aluminium oxide.
In the present invention, the cavity temperature for controlling the atomic layer deposition apparatus is preferably 230 DEG C~270 DEG C, more preferably
It it is most preferably 250 DEG C for 240 DEG C~260 DEG C.In the present invention, the intake manifold temperature of the atomic layer deposition apparatus is controlled
Preferably 100 DEG C~120 DEG C, more preferably 110 DEG C.In the present invention, described containing organic matter is preferably Al (CH3)3.At this
In invention, preferred pulse formula is passed through organic matter containing aluminium, and organic matter containing aluminium is made to be reacted with foamy graphite.In the present invention, pulsed
The pulse output cycle for being passed through the organic matter containing aluminium is preferably 80ms~120ms, and more preferably 90ms~110ms is most preferably
100ms.In the present invention, N is preferably used after obtaining reaction product2By unreacted reactant in reaction product (foamy graphite,
Organic matter containing aluminium, catalyst etc.) purging drying.In the present invention, the N2Purge time be preferably 4min~6min, it is more excellent
Elect 5min as.
It is reacted in the present invention, it is preferred to which pulsed is passed through water with the reaction product, makes the growth oxidation of foamy graphite surface
Aluminium.In the present invention, the pulse output cycle that pulsed is passed through water is preferably 80ms~120ms, and more preferably 90ms~
110ms is most preferably 100ms.In the present invention, the cycle period that pulsed is passed through water is preferably the cycle in 38 cycles~42, more
Preferably 40 cycles.
Carbon structure collector provided by the invention includes being attached to the carbon nanotubes on the alumina layer surface.In the present invention
In, the diameter of the carbon nanotubes is preferably 10nm~30nm, more preferably 15nm~25nm, is most preferably 20nm.In this hair
In bright, the preparation method of the carbon nanotubes is preferably：
Carbon nanotubes is grown using chemical vapour deposition technique on the alumina layer surface.
In the present invention, the temperature of the chemical vapour deposition technique growth carbon nanotubes is preferably 700 DEG C~900 DEG C, more
Preferably 750 DEG C~850 DEG C, be most preferably 800 DEG C.The present invention is to the specific method of chemical vapour deposition technique growth carbon nanotubes
There is no special limitation, be preferably：
Carbon source postcooling is passed through to the alumina layer surface, obtains carbon nanotubes.
In the present invention, the carbon source is preferably ethylene.In the present invention, the flow for being passed through carbon source is preferably 200sccm
~500sccm, more preferably 400sccm.In the present invention, the time for being passed through carbon source is preferably 40 minutes~60 minutes,
More preferably 45 minutes~55 minutes, be most preferably 50 minutes.In the present invention, the speed of the cooling is preferably 8 DEG C/min
~12 DEG C/min, more preferably 10 DEG C/min.In the present invention, the cooling preferably cools down in Ar.In the present invention, it is described
The flow of Ar is preferably 250sccm~450sccm, more preferably 380sccm~420sccm, is most preferably 400sccm.At this
In invention, preferably the alumina layer is made annealing treatment before being passed through carbon source to the alumina layer.In the present invention, institute
The temperature of annealing is stated as 700 DEG C~900 DEG C, more preferably 750 DEG C~850 DEG C, be most preferably 800 DEG C.In the present invention,
The time of the annealing is preferably 80 minutes~100 minutes, more preferably 85 minutes~95 minutes, is most preferably 90 points
Clock.In the present invention, it is preferred in Ar and H2Under conditions of anneal.
In the present invention, the mass ratio of the carbon nanotubes and foamy graphite is preferably (2~4)：1, more preferably (2.5
~3.5)：1, it is most preferably 3:1.
In the present invention, the pore volume of the carbon structure collector is preferably 0.8cm3g-1~1.1cm3g-1, more preferably
0.9cm3g-1~1.09cm3g-1, it is most preferably 1cm3g-1~1.08cm3g-1.In the present invention, the hole of the carbon structure collector
Footpath distribution is preferably 2nm~3nm, more preferably 2.2nm~2.8nm, is most preferably 2.4nm~2.6nm.In the present invention, institute
The specific surface area for stating carbon structure collector is preferably 230m2g-1~270m2g-1, more preferably 240m2g-1~260m2g-1, it is optimal
Elect 252m as2g-1.In the present invention, the higher absolute face electricity that can be reduced in electrode of the specific surface area of the carbon structure collector
Current density.
In the present invention, the preparation method of the carbon structure collector is preferably：
In foamy graphite surface deposited catalyst, catalyst layer is formed；
In the catalyst layer surface using atomic layer deposition method deposition of aluminium oxide, alumina layer is formed；
Carbon nanotubes is grown using chemical vapour deposition technique on the alumina layer surface, obtains carbon structure collector.
In the present invention, the preparation of deposition method, alumina layer of the catalyst and the growing method of carbon nanotubes
The preparation method of deposition method, alumina layer and the growing method of carbon nanotubes with the catalyst described in above-mentioned technical proposal
Unanimously, details are not described herein.
In the present invention, the carbon nanotubes of chemical vapour deposition technique growth is parallel, is arranged closely together to form carbon nanometer
Pipe array, this carbon nanotubes is seamless to be covalently grown in the surface of foamy graphite.In the present invention, the dimension limit of lithium deposit
Carbon nano pipe array is limited to, the Li dendrite for piercing through membrane will not be formed.
In the present invention, can carbon nanotubes and bubble be controlled by the condition that chemical vapour deposition technique is controlled to grow carbon nanotubes
The mass ratio of foam graphite.
The present invention provides a kind of battery cathode, including：
Carbon structure collector described in above-mentioned technical proposal；
The lithium metal being attached on the carbon structure collector.
In the present invention, the carbon structure collector is consistent with the carbon structure collector described in above-mentioned technical proposal, herein
It repeats no more.In the present invention, the preparation method of the battery cathode is preferably：
Using carbon structure collector as cathode, lithium piece is deposited lithium piece using the method for electrochemistry electro-deposition as anode
On carbon structure collector, battery cathode is obtained.
In the present invention, the current density in the electrochemistry electrodeposition process is preferably 0.25mA/cm2~2mA/cm2,
More preferably 0.5mA/cm2.In the present invention, when the time of the electrochemistry electro-deposition is preferably 5 small~40 it is small when, more preferably
For 8 it is small when~30 it is small when, be most preferably 10 it is small when~20 it is small when.
The present invention provides a kind of anode, including the carbon structure collector described in above-mentioned technical proposal.In the present invention
In, the preparation method of the positive electrode is preferably：
Sulphur powder and carbon structure collector are mixed in a solvent, obtain positive electrode.
In the present invention, the solvent is preferably toluene.In the present invention, the temperature of the mixing be preferably 150 DEG C~
160 DEG C, more preferably 155 DEG C.In the present invention, when the time of the mixing is preferably 8 small~12 it is small when, it is more preferably 10 small
When.
The present invention provides a kind of lithium battery, including the battery cathode and/or anode described in above-mentioned technical proposal.
In the present invention, the lithium battery is the high accumulator of a kind of safe, long lifespan, energy density.In the present invention, the lithium
Battery is preferably lithium metal secondary battery lithium-sulfur cell.In the present invention, the anode of the lithium battery is preferably above-mentioned skill
Anode described in art scheme.In the present invention, the battery cathode of the lithium battery is preferably described in above-mentioned technical proposal
Battery cathode.In the present invention, the solution of the electrolyte of the lithium battery is preferably 1,3- dioxolanes and 1,2- dimethoxy
Ethane.In the present invention, the volume ratio of 1, the 3- dioxolanes and 1,2- dimethoxy-ethane is preferably (0.5~1.5):1,
More preferably (0.8~1.2):1, it is most preferably 1:1.In the present invention, the solute of the electrolyte is preferably double fluoroforms
Sulfimide lithium.In the present invention, the solute concentration of the electrolyte is preferably 0.5mol/L~1.5mol/L, more preferably
0.8mol/L~1.2mol/L is most preferably 1mol/L.In the present invention, the additive of the lithium battery is preferably LiNO3.
In the present invention, the mass content of the additive in the electrolytic solution is preferably 0.8%~1.2%, and more preferably 1%.
The present invention does not have the method for the lithium battery special limitation, according to method well known to those skilled in the art into
Row battery assembles.
Cyclical stability test is carried out to the battery cathode of lithium battery provided by the invention, test result is, using this hair
The carbon structure collector of bright offer as storage lithium skeleton lithium battery cycle 800 it is small when after, polarizing voltage rises to from 4.8mv
10mv, battery is without short-circuit sign；Battery cathode and anode assembling to lithium battery provided by the invention help battery,
78% initial capacity is still kept after 400 circle of Xun Huan, the coulombic efficiency in cyclic process is up to 99.8%.
Raw material used in following embodiment of the present invention is commercial goods.
Embodiment 1
Nickel foam is put into high temperature process furnances, in Ar (400sccm) and H2Under the mixed airflow of (50sccm), normal pressure item
1050 DEG C are warming up under part, then keeps 1050 DEG C to anneal 30 minutes；CH is passed through into the nickel foam after annealing4(50sccm)5
Minute, it is then cooled to room temperature in the atmosphere of Ar (400sccm) with the speed of 10 DEG C/min, graphite is deposited in nickel foam
Alkene；The nickel foam that deposited graphene is put into the electrolyte of the nickel chloride containing 1mol/L except nickel, in constant voltage mode 2.2V
It under voltage, is electrolysed 10 minutes, after electrolysis completely, obtained electrolysate is rinsed several times repeatedly with deionized water and with ethyl alcohol,
Foamy graphite is obtained after 50 DEG C of oven drying.
The foamy graphite that the embodiment of the present invention 1 is prepared is observed, and the results are shown in Figure 1, and Fig. 1 is real for the present invention
Apply the picture for the foamy graphite that example 1 is prepared.
Density, thickness and the hole for the foamy graphite that the test embodiment of the present invention 1 is prepared, test result are sheet
The density for the foamy graphite that inventive embodiments 1 are prepared is 3mg/cm3, thickness 2mm, hole 110ppi.
Embodiment 2
The foamy graphite that embodiment 1 is prepared is put into a small-sized ion sputtering instrument, controls ion sputtering instrument
The in vivo pressure of chamber is 4Pa, electric current 15mA, sedimentation time 300s, and one layer of Fe conduct is sputtered in foamy graphite surface ion
Catalyst obtains catalyst layer.
The catalyst layer is put into atomic layer deposition (ALD) equipment, ALD equipment is adjusted, cavity temperature is arranged to
250 DEG C, intake manifold temperature is arranged to 110 DEG C, Al (CH3)3Presoma is maintained at room temperature, and pulsed is passed through Al (CH3)3
(100ms) is until Al (CH3)3It is reacted completely with all sites on foamy graphite, then uses high-purity N2(5min) is by remaining foam stone
Ink and reactant purging are clean, and then pulsed leads to enough H2O (100ms) enters in ald chamber, is allowed to and the in vivo reaction of chamber is produced
Object reacts, and goes out Al in the surface homoepitaxial of foamy graphite2O3, H is led to by the pulsed for cycling 40 cycles2O grows 5nm's
Al2O3, obtain alumina layer.
The alumina layer is put into tube furnace, in Ar (200sccm) and H2Under the mixed airflow of (100sccm), often
800 DEG C are warming up under the conditions of pressure, then keeps 800 DEG C to anneal 90 minutes, C is passed through into the alumina layer after annealing2H4
(400sccm) 50 minutes, is then cooled to room temperature in the atmosphere of Ar (200sccm) with the speed of 10 DEG C/min, is formed carbon and is received
Mitron obtains carbon structure collector.
The carbon structure collector that the embodiment of the present invention 2 is prepared is observed, the results are shown in Figure 2, and Fig. 2 is this hair
The picture for the carbon structure collector that bright embodiment 2 is prepared.
The diameter of carbon nanotubes, test result are in the carbon structure collector that the test embodiment of the present invention 2 is prepared, this
A diameter of 20nm of carbon nanotubes in the carbon structure collector that inventive embodiments 2 are prepared.
The mass ratio of carbon nanotubes and foamy graphite is 3 in the carbon structure collector that the embodiment of the present invention 2 is prepared:1.
The pore volume and specific surface area of carbon structure collector that the test embodiment of the present invention 2 is prepared, test result be,
The pore volume for the carbon structure collector that the embodiment of the present invention 2 is prepared is 1.1cm3g-1, specific surface area 252m2g-1。
Embodiment 3
Using electrochemical deposition method in 0.5mA cm-2The carbon structure collector that is prepared to embodiment 2 of current density
Surface lithium deposition, obtains battery cathode, and specific method is：
Carbon structure collector will be contained as cathode, metal lithium sheet assembles them into button cell or electrolysis as anode
Pond, using two (trimethyl fluoride sulfonyl) imine lithiums as electrolyte, solvent can be used in various common lithium ion batteries
Solvent, such as 1,3-dioxolane, 1,2- dimethoxy-ethanes, ethylene carbonate and diethyl carbonate etc..It is put using constant current
The method of electricity, in carbon junction steel collection liquid surface electro-deposition 10mAh cm-2Lithium metal obtains battery cathode.
The battery cathode that embodiment 3 is prepared is observed, and the results are shown in Figure 3, and Fig. 3 is the embodiment of the present invention 3
The battery cathode picture being prepared.
Embodiment 4
Lithium piece and carbon structure collector are assembled into symmetrical half-cell, specific method is：
Using the carbon structure collector that embodiment 2 is prepared as cathode, lithium piece is as anode, using volume ratio as 1:1
1,3-dioxolane and 1,2- dimethoxy-ethane are as electrolyte, two (trimethyl fluoride sulfonyls) of addition 1mol into electrolyte
Imines lithium electrolyte, using hollow glass fibre as membrane (in order to battery occur in the short period of time in cyclic process it is short
Road) battery assembling is carried out, battery assembling is using standard button cell CR2032.
Test the cyclical stability for the symmetrical half-cell being prepared：
First in 0.5mA cm-2Lithium metal when deposition 4 is small under electric current, then in 0.25mA cm-2Under electric current, to battery
First charge 2.5 it is small when discharge again 2.5 it is small when carry out constant current charge-discharge test.
Constant current charge-discharge test is carried out to the battery that the embodiment of the present invention 4 is prepared, test result is as shown in figure 4, Fig. 4
For the constant current charge-discharge curve for the battery that the embodiment of the present invention 4 is prepared, as shown in Figure 4, carbon structure collector and lithium are utilized
Symmetrical lithium/carbon structure collector battery that piece is assembled into cycle 800 it is small when after, although lagging voltage from 4.8 millivolts by
10 millivolts are gradually risen to, but battery does not have any sign display short circuit.By cycle 800 it is small when after scanning electron microscope
Photo, as shown in figure 5, scanning electron microscope (SEM) picture after the Symmetrical cells Xun Huan that Fig. 5, which is the embodiment of the present invention 4, to be prepared；
Battery cathode surface does not have any variation, without the appearance of Li dendrite.
Embodiment 5
Lithium piece and lithium paper tinsel are assembled into symmetrical half-cell, specific method is：
Using lithium paper tinsel as cathode, lithium piece is as anode, using volume ratio as 1:1 1,3- dioxolanes and 1,2- dimethoxys
Ethane is as electrolyte, two (trimethyl fluoride sulfonyl) imines lithium electrolytes of addition 1mol into electrolyte, with hollow glass
Fiber carries out battery assembling (in order to which short circuit occurs in the short period of time in cyclic process for battery) for membrane, and battery assembling is adopted
With standard button cell CR2032.
Test the cyclical stability for the symmetrical half-cell being prepared：
First in 0.5mA cm-2Lithium metal when deposition 4 is small under electric current, then in 0.25mA cm-2Under electric current, to battery
First charge 2.5 it is small when discharge again 2.5 it is small when carry out constant current charge-discharge test.
Lithium/lithium Symmetrical cells are gradually increasing in cyclic process polarizing voltage, and battery cycle 260 it is small when after occur
Short circuit.By cycle 350 when small after electron scanning micrograph, as shown in fig. 6, Fig. 6 is prepared into for the embodiment of the present invention 5
Scanning electron microscope (SEM) picture after the Symmetrical cells Xun Huan arrived；Battery cathode surface has substantial amounts of Li dendrite to occur.
Embodiment 6
Lithium piece and copper foil are assembled into symmetrical half-cell, specific method is：
Using copper foil as cathode, lithium piece is as anode, using volume ratio as 1:1 1,3- dioxolanes and 1,2- dimethoxys
Ethane is as electrolyte, two (trimethyl fluoride sulfonyl) imines lithium electrolytes of addition 1mol into electrolyte, with hollow glass
Fiber carries out battery assembling (in order to which short circuit occurs in the short period of time in cyclic process for battery) for membrane, and battery assembling is adopted
With standard button cell CR2032.
Test the cyclical stability for the symmetrical half-cell being prepared：
First in 0.5mA cm-2Lithium metal when deposition 4 is small under electric current, then in 0.25mA cm-2Under electric current, to battery
First charge 2.5 it is small when discharge again 2.5 it is small when carry out constant current charge-discharge test.
Lithium/copper Symmetrical cells spread of voltage in cyclic process.
From embodiment 4~6, bigger (the 252g cm of carbon structure collector specific surface area-3) electric current that causes its actual
The smooth collector of density ratio (such as copper foil, lithium paper tinsel) is much smaller so as to inhibiting the growth of Li dendrite, and carbon structure collector
Gap between upper carbon nanotubes further limits the growth of Li dendrite.
Embodiment 7
155 DEG C of hydro-thermals 10 of carbon structure collector that the toluene solution of the sulphur of 150g/L concentration and embodiment 2 are prepared
Hour, positive electrode is prepared；
The battery cathode that embodiment 3 is prepared is as cathode；
With the 1,3- dioxolanes of double trifluoromethanesulfonimide lithiums and 1,2- dimethoxyethane solutions (two of 1mol/L
The volume ratio of kind solution is 1:1) it is used as electrolyte；
LiNO3As additive, the LiNO3Mass fraction in the electrolytic solution is 1%；
Polypropylene screen is as membrane；
It is assembled into 2032 lithium-sulfur cells.
According to the method described in above-mentioned technical proposal, the electrification for the lithium-sulfur cell that the test embodiment of the present invention 7 is prepared
Performance is learned, as shown in Figure 7 and Figure 8, Fig. 7 is the charge and discharge for the first time for the lithium-sulfur cell that the embodiment of the present invention 7 is prepared to test result
Electric curve；Fig. 8 is the cycle-index-specific discharge capacity curve for the lithium-sulfur cell that the embodiment of the present invention 8 is prepared.By Fig. 7's
Charging and discharging curve can be seen that under the charge-discharge velocity of 2C, and the discharge capacity of lithium-sulfur cell is 1008mAh/g；By following for Fig. 8
After ring curve can be seen that 400 Xun Huans, the discharge capacity of lithium-sulfur cell is maintained at 790mAh/g, and coulombic efficiency is still protected
It holds more than 98%.
As seen from the above embodiment, the present invention provides a kind of carbon structure collector, including：Foamy graphite；It is attached to institute
State the alumina layer on foamy graphite surface；It is attached to the carbon nanotubes on the alumina layer surface.The present invention provides a kind of electricity
Pond cathode, including：Carbon structure collector described in above-mentioned technical proposal；The lithium metal being supported on the carbon structure collector.
The present invention provides a kind of lithium battery, including the battery cathode described in above-mentioned technical proposal.Carbon structure afflux provided by the invention
Body is preferentially filled up the hole of collector, avoids lithium metal using three-dimensional carbon material, lithium metal along carbon cannon born frame deposition growing
Point effect during planar growth.Therefore, carbon collector provided by the invention can effectively inhibit the growth of metal Li dendrite,
So that lithium battery has preferable cyclicity and security, also there is higher energy density.
Claims (10)
1. a kind of carbon structure collector, including：
Foamy graphite；
It is attached to the alumina layer on the foamy graphite surface；
It is attached to the carbon nanotubes on the alumina layer surface.
2. carbon structure collector according to claim 1, which is characterized in that the density of the foamy graphite is 3mg cm-3
~50mg cm-3。
3. carbon structure collector according to claim 1, which is characterized in that the thickness of the foamy graphite for 1.7mm~
1.9mm。
4. carbon structure collector according to claim 1, which is characterized in that the hole of the foamy graphite for 400 μm~
500μm。
5. carbon structure collector according to claim 1, which is characterized in that a diameter of 10nm of the carbon nanotubes~
30nm。
6. carbon structure collector according to claim 1, which is characterized in that the carbon nanotubes and the quality of foamy graphite
Than for (2~4)：1.
7. carbon structure collector according to claim 1, which is characterized in that the pore volume of the carbon structure collector is
0.8cm3g-1~1.1cm3g-1；
The specific surface area of the carbon structure collector is 230m2g-1~270m2g-1。
8. a kind of battery cathode, including：
Carbon structure collector in claim 1~7 described in any one；
It is attached to the lithium metal of carbon nano tube surface on the carbon structure collector.
9. a kind of anode, including the carbon structure collector described in any one in claim 1~7.
10. a kind of lithium battery, including the anode described in the battery cathode and/or claim 9 described in claim 8.
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| KR102093971B1 (en) * | 2017-06-21 | 2020-05-21 | 주식회사 엘지화학 | Lithium secondary battery |
| CN107910496B (en) * | 2017-10-09 | 2020-08-14 | 中南大学 | Metallic lithium cathode for secondary battery, preparation method and application thereof |
| CN110444767B (en) * | 2018-05-03 | 2021-12-10 | 中国科学技术大学 | Three-dimensional current collector for lithium metal negative electrode of primary/secondary battery, lithium metal negative electrode and primary/secondary battery |
| CN108832133A (en) * | 2018-06-14 | 2018-11-16 | 福建猛狮新能源科技有限公司 | A kind of flexible current-collecting body battery and its manufacturing method |
| CN111129504A (en) * | 2020-01-17 | 2020-05-08 | 清华大学深圳国际研究生院 | Preparation method of modified current collector, electrode plate and lithium battery |
| CN112086645A (en) * | 2020-09-21 | 2020-12-15 | 河南英能新材料科技有限公司 | Lithium battery negative pole piece |
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| CN114361412A (en) * | 2021-12-16 | 2022-04-15 | 江苏大学 | Multi-walled carbon nanotube negative electrode material and preparation method and application thereof |
| GB2622038A (en) * | 2022-08-31 | 2024-03-06 | Dyson Technology Ltd | Energy storage devices and components thereof |
| WO2024077473A1 (en) * | 2022-10-11 | 2024-04-18 | 宁德时代新能源科技股份有限公司 | Current collector and manufacturing method therefor, and electrode plate, secondary battery and electric apparatus |
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