CN108923024A - A kind of magnetism lithium metal battery copper magnetic combination electrode material and its preparation process and application - Google Patents
A kind of magnetism lithium metal battery copper magnetic combination electrode material and its preparation process and application Download PDFInfo
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- CN108923024A CN108923024A CN201810589120.8A CN201810589120A CN108923024A CN 108923024 A CN108923024 A CN 108923024A CN 201810589120 A CN201810589120 A CN 201810589120A CN 108923024 A CN108923024 A CN 108923024A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
The suitable technical field of lithium batteries of invention more particularly to a kind of magnetic lithium metal battery copper magnetic combination electrode material and its preparation process and application, the preparation process of the magnetism lithium metal battery copper magnetic combination electrode material includes following preparation step：1) then the oxide for removing Copper substrate surface cleans, is dry；2) magneto spheric structure containing magnetic metal is prepared on the Copper substrate surface handled through step 1)；Wherein, the magnetic metal includes iron, cobalt, nickel and platinum, and the magneto spheric structure includes magnetic coating structure, non magnetic micro-nano structure doped magnetic particle, magnetic micro-nano structure doped magnetic particle and magnetic micro-nano structure.
Description
Technical field
The suitable technical field of lithium batteries of invention more particularly to a kind of magnetic lithium metal battery copper magnetic combination electrode
Material and its preparation process and application.
Background technique
With electronic equipment, the fast development of electric car, lithium ion battery would become hard to meet people to battery performance
It is required that.And lithium anode decuples the theoretical capacity of conventional graphite cathode with it, i.e. the theoretical capacity of graphite cathode is
372mAh/g, and the theoretical capacity of lithium anode is up to 3860mAh/g, and most negative potential can reach -3.045V, much
More than the performance of graphite cathode, ideal next battery eliminator will be become.
But lithium metal battery, in practical study, there is also many problems.Maximum challenge is exactly dendritic growth
Problem.In lithium platingactive/stripping process, because nonuniform deposition will lead to Li dendrite preferred growth in certain particular crystal orientations.It crosses
The dendrite of degree growth will puncture through diaphragm, and positive and negative anodes is caused to be shorted.This more will lead to the thermal runaway of lithium metal battery, increase explosion with
And the risk of battery fire.
By the deposition process to optimization lithium, the uniform deposition of lithium can be promoted, the growth of dendrite inhibition improves cell performance
Energy.
To realize the optimization to lithium, solve the above problems, many researchers are by introducing various electrolysis additives
To inhibit the growth of Li dendrite.Such as lithium fluoride, lithium nitrate, lithium sulfide etc., in cyclic process, electrolyte and lithium metal it is anti-
Answer product that can form stable solid electrolyte interface (SEI), thus dendrite inhibition growth (Nat.Mater.2014,13,
961.).Archer teaches the nanosizing electrolyte that seminar's proposition is fixed with anion to improve the performance (Nano of cathode
Lett15(5):2910–2916.).Also keep lithium electro-deposition more uniform it has been proposed that constructing artificial SEI film, alleviate branch whereby
Brilliant growth (Nat.Nanotechnol.2016,11,626.).In addition, by high salt concentration electrolyte, (salinity is more than 2M's
Electrolyte system) unique ion conductance and viscosity number constrain the depositing behavior of lithium ion, reach high stable cycle performance
(J.Power Sources 2013,232,23-28).The structure design of lithium anode collector is recent study hot spot,
Specific surface area by increasing collector can inhibit lithium dendrite growth, the especially appearance of three-dimensional structure collector
(Advanced Functional Materials, 2017,27,1606422).The above method is all based on lithium metal and electrolysis
The regulation of liquid interface focuses on the modified aspect of electrolyte/matter, SEI film etc., achieves many valuable research achievements, but big
It is all the test carried out at low range (such as 0.5mA/cm2), and cycle-index is limited.Therefore, from practical application, there are also very big
Distance, still need to further investigate to meet the requirement of high-performance lithium base battery.
The entire reaction process of lithium-base battery body is：When charging, lithium ion is moved to cathode from anode and electrocrystallization occurs
I.e. lithium metal deposits；When electric discharge, the lithium metal on cathode loses electronics and is oxidized to the i.e. lithium metal removing of lithium ion, moves again to just
Pole.In battery system, the movement of shuttling due to lithium ion in positive and negative interpolar forms a stable electric field.To the electricity
The regulation of field will affect the electrocrystallization process of lithium metal, and then can inhibit the formation and growth of Li dendrite.It is well known that electric field
It influences each other with magnetic field energy, acting on internal electric field by externally-applied magnetic field may be implemented the effective of metallic crystal process
Control, such as electromagnetic agitation casting can substantially reduce dendrite, thinning microstructure.Equally, the electrochemical deposition under magnetic fields is also
Recent study hot spot, principle are based on magnetohydrodynamics effect (effect of the conductive fluid by Lorentz force) and magnetizing force
Effect etc., the influence to the mass transfer of electro-deposition, electrode reaction, electrocrystallization process etc., pattern, the knot of final optimization pass deposited metal layer
Structure and performance.Since the energy transmission mode that magnetic field has energy density high and easy to control, contactless, and alternative are big
The advantages that, so that magnetoelectricity chemical deposition has become the emerging technology of material preparation.Research shows that electro-deposition preparation Cu, Ni, Co,
Whens Ni-Fe, Ni-Mo, Co-W-Cu etc., externally-applied magnetic field can significantly refine crystal grain, obtain fine and close institutional framework, and can influence
Crystal orientation, that is, the texture of (enhancing or decrease) metal deposition layer and dendritic growth direction or even dendrite inhibition.
Patent Office of the People's Republic of China discloses a kind of cathode for lithium metal battery and the lithium including it on November 24th, 2017
The application for a patent for invention of metal battery applies for notification number CN107394115A, prepares protective layer on the metal lithium electrode,
The protective layer is with 106Pa or bigger Young's modulus and including having greater than 1 μm to about 100 μm or smaller granularity
At least one of free organic granular, inorganic particle and organic/inorganic particle, protect metal lithium electrode and avoid lithium
Dendrite is generated when metal deposit, actually progress protective layer, the influence generated when depositing to lithium metal is smaller, can not effectively realize
Inhibition to dendrite, and its lithium metal crystal compactness extent formed is low.
Summary of the invention
In order to solve in the prior art in lithium platingactive/stripping process, because nonuniform deposition will lead to Li dendrite certain
Preferred growth in particular crystal orientation.The dendrite of undue growth will puncture through diaphragm, and positive and negative anodes is caused to be shorted, and then lead to lithium metal battery
Thermal runaway, the problem of increasing the risk of explosion and battery fire, the present invention provides a kind of magnetic lithium metal battery copper magnetic
Combination electrode material and its preparation process, it is heavy that the magnetic field generated by prepared combination electrode material generates induction to lithium ion
Product effect, can effectively dendrite inhibition growth, improve the cyclical stability and security performance of lithium battery.
It is a further object of the present invention to provide a kind of applications of magnetic lithium metal battery copper magnetic combination electrode material, i.e., by it
It is used as the negative electrode material in magnetic lithium metal battery.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation process of magnetism lithium metal battery copper magnetic combination electrode material, the preparation process include following preparation step
Suddenly：
1) then the oxide for removing Copper substrate surface cleans, is dry；
2) magneto spheric structure containing magnetic metal is prepared on the Copper substrate surface handled through step 1)；
Wherein, the magnetic metal includes iron, cobalt, nickel and platinum, and the magneto spheric structure includes magnetic coating structure, non magnetic micro-nano knot
Structure doped magnetic particle, magnetic micro-nano structure doped magnetic particle and magnetic micro-nano structure.
Preferably, the preparation process of the magnetic coating structure includes following preparation step：
A1 acid mixed solution) is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：
The molar concentration of the sulfuric acid is 0.1~2mol/L；
The molar concentration of the ammonium chloride is 0.75~7.5mol/L；
Soluble metal compound is added in oxytropism mixed liquor again, is configured to electrodeposit liquid：
Wherein, soluble metal compound is soluble magnetic metal compound, and it meets following conditions：
The magnetic metal ion molar concentration that the solubility magnetic metal compound introduces is 0.2~2.0mol/L；
A2 made with step A1) using platinum or graphite as to electrode) using Copper substrate obtained by step 1) as working electrode
The electrodeposit liquid obtained carries out electro-deposition as the solution system of electro-deposition, and control electro-deposition voltage is -0.1~-2.0V, and electric current is close
Degree is -100~-500A/m2, sedimentation time is 10~300s, is dried after washing in 40~150 DEG C, obtains surface and plates with magnetic
The Copper substrate of layer structure is to get to magnetic lithium metal battery copper magnetic combination electrode material.
Preferably, described the step of preparing non magnetic micro-nano structure doped magnetic particle, includes：
B1 copper micro-nano structure) is prepared on the Copper substrate surface handled through step 1), obtains composite construction Copper substrate；
B2 acid mixed solution) is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：
The molar concentration of the sulfuric acid is 0.1~2mol/L；
The molar concentration of the ammonium chloride is 0.75~7.5mol/L；
Soluble magnetic metal compound is added in oxytropism mixed liquor again, is configured to the electrodeposit liquid of the ingredient containing magnetic metal,
In the electrodeposit liquid of the ingredient containing magnetic metal：
The magnetic metal ion molar concentration that the solubility magnetic metal compound introduces is 0.05~4.0mol/L；
B3) using composite construction Copper substrate obtained by step B1) as working electrode, using platinum or graphite as to electrode, with step
Rapid B2) obtained by the electrodeposit liquid of the ingredient containing magnetic metal carry out electro-deposition as the solution system of electro-deposition, it is heavy to control electricity
Product voltage is -0.1~-2.0V, and current density is -100~-500A/m2, sedimentation time is 10~300s, after washing in 40~
150 DEG C of drying obtain Copper substrate of the surface with non magnetic micro-nano structure doped magnetic particle to get magnetic lithium metal battery is arrived
Copper magnetic combination electrode material.
Preferably, the step of preparation magnetism micro-nano structure doped magnetic particle, includes：
C1 magnetic micro-nano structure) is prepared on the Copper substrate surface handled through step 1), obtains magnetic coupling structure Copper substrate, wherein
Magnetic micro-nano structure is the micro-nano structure of the ingredient containing magnetic metal；
C2 acid mixed solution) is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：
The molar concentration of the sulfuric acid is 0.1~2mol/L；
The molar concentration of the ammonium chloride is 0.75~7.5mol/L；
Soluble magnetic metal compound is added in oxytropism mixed liquor again, is configured to the electrodeposit liquid of the ingredient containing magnetic metal,
In the electrodeposit liquid of the ingredient containing magnetic metal：
The magnetic metal ion molar concentration that the solubility magnetic metal compound introduces is 0.05~4.0mol/L；
C3) using magnetic coupling structure Copper substrate obtained by step C1) as working electrode, using platinum or graphite as to electrode,
Electro-deposition, control are carried out using the electrodeposit liquid of the ingredient containing magnetic metal obtained by step C2) as the solution system of electro-deposition
Electro-deposition voltage is -0.1~-2.0V, and current density is -100~-500A/m2, sedimentation time be 10~300s, after washing in
40~150 DEG C of drying, obtaining surface has the Copper substrate of magnetic micro-nano structure doped magnetic particle to get magnetic lithium metal electricity is arrived
Pond copper magnetic combination electrode material.
Preferably, the step of preparation magnetism micro-nano structure, includes：
D1) in the micro-nano structure of the Copper substrate surface preparation ingredient containing magnetic metal handled through step 1), in 40~150 after washing
DEG C drying, obtaining surface has the Copper substrate of magnetic micro-nano structure to get to magnetic lithium metal battery copper magnetic combination electrode material.
The magnetism lithium metal battery copper magnetic combination electrode material prepares magnetosphere on Copper substrate surface using copper as matrix
Structure, magneto spheric structure are magnetic coating structure, non magnetic micro-nano structure doped magnetic particle, magnetic micro-nano structure doped magnetic particle
With any one in magnetic micro-nano structure, by produced by magneto spheric structure, formed stable micro- magnetic field, in lithium metal battery
Good guiding role is generated when middle lithium deposition, so that lithium metal generates dense packing, while causing the disturbance i.e. magnetic of electrolyte
Hydrodynamics effect strengthens mass transfer, reduces concentration polarization, promotes forming core, the formation and growth of dendrite inhibition.
Preferably, step A2), step B3) and step C3) electrodeposition process control electro-deposition voltage is -0.1
~-1.2V, current density are -200~-400A/m2, sedimentation time is 60s~100s.
A kind of magnetism lithium metal battery copper magnetic combination electrode material, the copper magnetic combination electrode material using copper as matrix,
And the magneto spheric structure containing magnetic metal is prepared on Copper substrate surface, the magnetic metal includes iron, cobalt, nickel and platinum.
Preferably, the magneto spheric structure include magnetic coating structure, it is non magnetic micro-nano structure doped magnetic particle, magnetic micro-
Micro-nano structure doped magnetic particle and magnetic micro-nano structure.
A kind of magnetic lithium metal battery comprising the magnetic lithium metal battery copper magnetic combination electrode material, feature exist
In the negative electrode material of the magnetism lithium metal battery is copper magnetic combination electrode material, molten with bis- (trifyl) imine lithiums
Liquid is as electrolyte, using high molecular material as diaphragm.
Preferably, the molar concentration of (trifyl) imine lithiums bis- in the electrolyte is 0.5~2mol/L, institute
Stating diaphragm is polypropylene diaphragm.
Magnetic lithium metal battery using magnetic lithium metal battery copper magnetic combination electrode material as negative electrode material, using copper as
Matrix, and prepare magneto spheric structure on Copper substrate surface, by produced by magneto spheric structure, stable micro- magnetic field for being formed, in lithium gold
Guidance lithium metal ion generates the deposition of orientation when belonging to lithium deposition in battery, avoids lithium metal ion in conventional lithium metal battery
It is disorderly and unsystematic when deposition, it is loose to lead to occur coarse grains, dendritic growth and accumulation, so that lithium metal generates fine and close heap
Product, while causing the disturbance i.e. magnetohydrodynamics effect of electrolyte, strengthen mass transfer, reduce concentration polarization, promote forming core, inhibits branch
Brilliant formation and growth, improves the service life and using effect of lithium metal battery.
Wherein, the magneto spheric structure of magnetic coating structure have that any surface finish, micro- magnetic field generate magnetic force is stronger, guide effect more
Add the advantages that outstanding, reinforcing mass transfer effect caused by gas is the most obvious, and non magnetic micro-nano structure doped magnetic particle, magnetism are micro-
Micro-nano structure doped magnetic particle and magnetic micro-nano structure all have great specific surface area, itself strengthens battery effect,
The lithium metal dense packing effect that micro- magnetic field of non magnetic micro-nano structure doped magnetic particle generates is best, and magnetic micro-nano structure is mixed
The magnetohydrodynamics effect that miscellaneous magnetic-particle generates is most strong, and effect caused by magnetic micro-nano structure is between the two.
The beneficial effects of the invention are as follows：
1) lithium anode local current densities, lithium forming core overpotential and interface impedance are reduced；
2) the micro- magnetic field generated is conducive to the transmission of electronics and ion, reduces battery system impedance；
3) inhibit Li dendrite method ratio with conventional, do not change the battery systems such as electrolyte, diaphragm using copper magnetic combination electrode material
It constitutes, negative effect is not had to battery comprehensive performance；
4) micro-nano structure can accommodate the deposition of lithium metal, provide expansion space release stress, and can store more electrolyte；
5) the micro- magnetic field generated generates Lorentz force effect to the lithium ion of movement, and spiral acceleration deposits to negative terminal surface, so that
Dense packing metal crystalline lithium in copper magnetic combination electrode material frame, while the disturbance i.e. magnetohydrodynamics of electrolyte being caused to be imitated
It answers, strengthens mass transfer, reduce concentration polarization, promote forming core, the formation and growth of dendrite inhibition.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for the copper magnetic combination electrode material that surface is prepared with three-dimensional ordered macroporous structure；
Fig. 2 is the mechanism figure of electrode material discharge process prepared by the present invention；
Fig. 3 is the scanning electricity after electrode material and plane copper negative electrode material circulation prepared by embodiment 1 after loop test
Mirror sectional view；
Fig. 4 is the scanning electricity after electrode material and plane copper negative electrode material circulation prepared by embodiment 1 after loop test
Mirror plane figure；
Fig. 5 is the scanning electron microscope (SEM) photograph for the copper magnetic combination electrode material that surface is prepared with nanowire structure；
Fig. 6 is the scanning electron microscope (SEM) photograph for the copper magnetic combination electrode material that surface is prepared with nanometer band structure；
Fig. 7 is the scanning electron microscope (SEM) photograph of surface preparation and nano wire and the copper magnetic combination electrode material of nanometer sheet composite construction.
Specific embodiment
Embodiment 1
By poly (methyl methacrylate) micro-sphere and water with mass ratio for 50：250 ratio mixing, it is stand-by to stir into lotion；By institute
Lotion, water and polyethylene glycol obtained are with volume ratio 20：400：2 ratio mixing, obtains electro-deposition after ultrasonic disperse or stirring
Liquid；It is heavy that electricity is carried out using above-mentioned electrodeposit liquid as solution system using platinum as to electrode using tabula rasa Copper substrate as working electrode
Product, control electro-deposition voltage are 4V, and electric current 0.006A, sedimentation time 45s are obtained to surface and be covered with poly-methyl methacrylate
The tabula rasa Copper substrate of ester microsphere template.By water and diammonium hydrogen citrate with mass ratio 100：2 ratio mixing, stirs into uniform
Mixed liquor, soluble copper salt cupric pyrophosphate is added into mixed liquor and sodium pyrophosphate stirring is configured to cupric electrodeposit liquid, wherein：
Copper ion concentration is 0.4mol/L in cupric electrodeposit liquid；The concentration of acid ion pyrophosphate is in cupric electrodeposit liquid
0.8mol/L.Gained surface is covered with the tabula rasa Copper substrate of poly (methyl methacrylate) micro-sphere template as working electrode, with
Platinum is used as to electrode, using calomel electrode as reference electrode, solution system of the prepared cupric electrodeposit liquid as electro-deposition
Carry out electro-deposition, control electro-deposition current density be 6mAcm-2, control electrodeposition time be 200s, after electro-deposition with
The mode of dissolution or calcination obtains composite construction copper after removing poly (methyl methacrylate) micro-sphere, i.e. surface has three-dimensional order big
The Copper substrate of pore structure, as shown in Figure 1.Acid mixed solution is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：The sulphur
The molar concentration of acid is 0.5mol/L；The molar concentration of the ammonium chloride is 1mol/L；Chlordene is added in oxytropism mixed liquor again
Platinic acid and nickel nitrate, are configured to platinum electrodeposition of nickel liquid, in platinum electrodeposition of nickel liquid：The platinum ion mole that the chloroplatinic acid introduces is dense
Degree is 0.05mol/L；The nickel ion molar concentration that the nickel nitrate introduces is 0.2mol/L；Using composite construction copper obtained as
Working electrode, using platinum as to electrode, resulting platinum electrodeposition of nickel liquid carries out electro-deposition, control as the solution system of electro-deposition
Electro-deposition voltage is -1.2V, and current density is -300A/m2, sedimentation time 60s, is dried after washing in 60 DEG C, after magnetization
To the composite construction copper of carrying magnetic particle, i.e., magnetic lithium metal battery copper magnetic combination electrode material；By 1,3-dioxolane and 1,
2- dimethoxy-ethane is with volume ratio 1：1 volume ratio is configured to base fluid, will be bis- (trifyl) imine lithium be dissolved in base fluid
In be made electrolyte, in electrolyte：The molar concentration of bis- (trifyl) imine lithiums is 1mol/L；With prepared electrolysis
Matter, obtained magnetic lithium metal battery copper magnetic combination electrode material and polypropylene diaphragm are material in the glove box that argon gas is housed
In be assembled into CR2025 button cell to get to the magnetic lithium battery.Above-mentioned battery is subjected to electro-chemical test discovery,
1mA/cm2Under current density, without dendritic growth in 300 circles, coulombic efficiency is up to 98.8%.Battery dismantling after circulation 10 is enclosed
SEM characterization is carried out afterwards, and such as Fig. 3,4, lithium deposits layer surface even compact, no dendritic growth.Its discharge procedure mechanism figure such as Fig. 2 institute
Show, scanning electron microscope (SEM) photograph is shown as shown in Figure 1, Figure 3 and Figure 4.
Embodiment 2
By spherex, chitosan microball and water with mass ratio for 50：250 ratio mixing, it is stand-by to stir into lotion；It will be made
Lotion, water and the polyethylene glycol obtained is with volume ratio 10：300：1 ratio mixing, obtains electrodeposit liquid after ultrasonic disperse or stirring；
Electro-deposition is carried out using above-mentioned electrodeposit liquid as solution system using platinum as to electrode using tabula rasa Copper substrate as working electrode,
Control electro-deposition voltage is 1.0V, and electric current 0.001A, sedimentation time 10s are obtained to surface and be covered with spherex, chitosan
The tabula rasa Copper substrate of microballoon template.By water and Potassium Hydrogen Phthalate with mass ratio 100：1 ratio mixing, stirs into uniform
Mixed liquor, soluble copper salt cupric pyrophosphate is added into mixed liquor and sodium pyrophosphate stirring is configured to cupric electrodeposit liquid, wherein：
Copper ion concentration is 0.2mol/L in cupric electrodeposit liquid；The concentration of acid ion pyrophosphate is in cupric electrodeposit liquid
0.5mol/L.Gained surface is covered with the tabula rasa Copper substrate of spherex, chitosan microball template as working electrode, with platinum
As to electrode, using calomel electrode as reference electrode, prepared cupric electrodeposit liquid as electro-deposition solution system into
Row electro-deposition, control electro-deposition current density are 2mAcm-2, and control electrodeposition time is 100s, with molten after electro-deposition
Solution or the mode of calcination obtain composite construction copper after removing spherex, chitosan microball.With sulfuric acid, ammonium chloride and water preparating acid
Property mixed liquor, in acid mixed solution：The molar concentration of the sulfuric acid is 0.1mol/L；The molar concentration of the ammonium chloride is
0.75mol/L；Sodium platinate and nickel sulfate is added in oxytropism mixed liquor again, is configured to platinum electrodeposition of nickel liquid, platinum electrodeposition of nickel liquid
In：The platinum ion molar concentration that the sodium platinate introduces is 0.05mol/L；The nickel ion molar concentration that the nickel sulfate introduces is
0.2mol/L；Using composite construction copper obtained as working electrode, using platinum as to electrode, resulting platinum electrodeposition of nickel liquid conduct
The solution system of electro-deposition carries out electro-deposition, and control electro-deposition voltage is -0.1V, and current density is -100A/m2, sedimentation time
For 10s, is dried after washing in 40 DEG C, the composite construction copper of carrying magnetic particle is obtained after magnetization, i.e., magnetic lithium metal battery copper magnetic
Combination electrode material；By 1,3-dioxolane and 1,2- dimethoxy-ethane is with volume ratio 1：0.8 volume ratio is configured to base fluid,
Will be bis- (trifyl) imine lithium be dissolved in base fluid electrolyte be made, in electrolyte：Bis- (trifyl) imine lithiums
Molar concentration be 0.5mol/L；With prepared electrolyte, obtained magnetic lithium metal battery copper magnetic combination electrode material
It is that material is assembled into CR2025 button cell in the glove box equipped with argon gas to get golden to the magnetic lithium with polypropylene diaphragm
Belong to battery.Above-mentioned battery is subjected to electro-chemical test discovery, in 1mA/cm2Under current density, without dendritic growth, library in 300 circles
Human relations efficiency is up to 96.9%.Its discharge procedure mechanism figure is as shown in Figure 2.
Embodiment 3
By albumin microsphere, polystyrene microsphere and polyacrylic acid microballoon and water with mass ratio for 100：350 ratio mixing, is stirred
It is stand-by to mix lotion；By obtained lotion, water and polyethylene glycol with volume ratio 30：700：3 ratio mixing, ultrasonic disperse or
Electrodeposit liquid is obtained after stirring；Using tabula rasa Copper substrate as working electrode, using platinum as to electrode, using above-mentioned electrodeposit liquid as
Solution system carries out electro-deposition, and control electro-deposition voltage is 7.0V, and electric current 0.02A, sedimentation time 90s are obtained to surface and covered
It is stamped the tabula rasa Copper substrate of albumin microsphere, polystyrene microsphere and polyacrylic acid microballoon template.By water and diammonium hydrogen citrate
With mass ratio 100：5 ratio mixing, stir into uniform mixed liquor, into mixed liquor be added soluble copper salt cupric pyrophosphate and
Sodium pyrophosphate stirring is configured to cupric electrodeposit liquid, wherein：Copper ion concentration is 0.8mol/L in cupric electrodeposit liquid；Cupric electricity
The concentration for depositing acid ion pyrophosphate in liquid is 7.5mol/L.Gained surface is covered with albumin microsphere, polystyrene
The tabula rasa Copper substrate of microballoon and polyacrylic acid microballoon template is as working electrode, using platinum as to electrode, using calomel electrode as
Reference electrode, prepared cupric electrodeposit liquid carry out electro-deposition as the solution system of electro-deposition, and control electro-deposition electric current is close
Degree is 10.0mAcm-2, and control electrodeposition time is 700s, removes white egg in a manner of dissolution or calcination after electro-deposition
Composite construction copper is obtained after Bai Weiqiu, polystyrene microsphere and polyacrylic acid microballoon.It is prepared with sulfuric acid, ammonium chloride and water acid mixed
Liquid is closed, in acid mixed solution：The molar concentration of the sulfuric acid is 2mol/L；The molar concentration of the ammonium chloride is 7.5mol/L；
Iron chloride and cobalt chloride is added in oxytropism mixed liquor again, is configured to iron cobalt electrodeposit liquid, in iron cobalt electrodeposit liquid：The chlorination
The iron ion molar concentration that iron introduces is 0.5mol/L；The nickel ion molar concentration that the cobalt chloride introduces is 0.5mol/L；It will
Composite construction copper obtained is as working electrode, and using platinum as to electrode, resulting iron cobalt electrodeposit liquid is as the molten of electro-deposition
Liquid system carries out electro-deposition, and control electro-deposition voltage is -2.0V, and current density is -500A/m2, sedimentation time 300s, washing
It is dried afterwards in 150 DEG C, the composite construction copper of carrying magnetic particle is obtained after magnetization, i.e., magnetic lithium metal battery copper magnetic combination electrode material
Material；By 1,3-dioxolane and 1,2- dimethoxy-ethane is with volume ratio 1：1.5 volume ratio is configured to base fluid, by bis- (trifluoros
Mesyl) imine lithium is dissolved in base fluid and electrolyte is made, in electrolyte：The molar concentration of bis- (trifyl) imine lithiums
For 2mol/L；With prepared electrolyte, obtained magnetic lithium metal battery copper magnetic combination electrode material and polypropylene diaphragm
CR2025 button cell is assembled into the glove box equipped with argon gas for material to get the magnetic lithium metal battery is arrived.It will be upper
It states battery and carries out electro-chemical test discovery, under 1mA/cm2 current density, without dendritic growth in 300 circles, coulombic efficiency is up to
97.4%.Its discharge procedure mechanism figure is as shown in Figure 2.
Embodiment 4
By gelatine microsphere and water with mass ratio for 50：250 ratio mixing, it is stand-by to stir into lotion；By obtained lotion, water
With polyethylene glycol with volume ratio 20：400：2 ratio mixing, obtains electrodeposit liquid after ultrasonic disperse or stirring；Tabula rasa is copper-based
Body carries out electro-deposition for above-mentioned electrodeposit liquid as solution system, controls electro-deposition as working electrode using platinum as to electrode
Voltage is 2.5V, electric current 0.005A, sedimentation time 30s, obtains to surface and is covered with the tabula rasa Copper substrate of gelatine microsphere template.
By water and diammonium hydrogen citrate with mass ratio 100：2 ratio mixing, stirs into uniform mixed liquor, being added into mixed liquor can
Dissolubility mantoquita cupric pyrophosphate and sodium pyrophosphate stirring are configured to cupric electrodeposit liquid, wherein：Copper ion is dense in cupric electrodeposit liquid
Degree is 0.4mol/L；The concentration of acid ion pyrophosphate is 0.8mol/L in cupric electrodeposit liquid.Gained surface is covered with
The tabula rasa Copper substrate of gelatine microsphere template is as working electrode, using platinum as to electrode, using calomel electrode as reference electrode, institute
The cupric electrodeposit liquid of preparation carries out electro-deposition as the solution system of electro-deposition, and control electro-deposition current density is 4.0mA
Cm-2, control electrodeposition time are 200s, are answered after removing gelatine microsphere in a manner of dissolution or calcination after electro-deposition
Close structure copper.Acid mixed solution is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：The molar concentration of the sulfuric acid is
0.5mol/L；The molar concentration of the ammonium chloride is 1mol/L；Cobalt chloride and nickel chloride is added in oxytropism mixed liquor again, prepares
At cobalt electrodeposition of nickel liquid, in cobalt electrodeposition of nickel liquid：The cobalt ions molar concentration that the cobalt chloride introduces is 0.05mol/L；It is described
The nickel ion molar concentration that nickel chloride introduces is 0.2mol/L；Using composite construction copper obtained as working electrode, using platinum as
To electrode, resulting cobalt electrodeposition of nickel liquid as electro-deposition solution system carry out electro-deposition, control electro-deposition voltage be-
0.1V, current density are -200A/m2, sedimentation time 60s, dry after washing in 60 DEG C, carrying magnetic particle is obtained after magnetization
Composite construction copper, i.e., magnetic lithium metal battery copper magnetic combination electrode material；By 1,3-dioxolane and 1,2- dimethoxy-ethane
With volume ratio 1：1 volume ratio is configured to base fluid, will be bis- (trifyl) imine lithium be dissolved in base fluid electrolyte be made, electricity
Xie Zhizhong：The molar concentration of bis- (trifyl) imine lithiums is 1mol/L；With prepared electrolyte, obtained magnetism
Lithium metal battery copper magnetic combination electrode material and polypropylene diaphragm are that material is assembled into CR2025 in the glove box equipped with argon gas
Button cell is to get to the magnetic lithium metal battery.Above-mentioned battery is subjected to electro-chemical test discovery, in 1mA/cm2 electric current
Under density, without dendritic growth in 300 circles, coulombic efficiency is up to 98.1%.Its discharge procedure mechanism figure is as shown in Figure 2.
Embodiment 5
By polylactic acid microsphere and water with mass ratio for 50：250 ratio mixing, it is stand-by to stir into lotion；By obtained lotion,
Water and polyethylene glycol are with volume ratio 20：400：2 ratio mixing, obtains electrodeposit liquid after ultrasonic disperse or stirring；By tabula rasa copper
Matrix carries out electro-deposition for above-mentioned electrodeposit liquid as solution system, it is heavy to control electricity as working electrode using platinum as to electrode
Product voltage is 5.0V, electric current 0.015A, sedimentation time 60s, obtains to surface and is covered with the tabula rasa copper of polylactic acid microsphere template
Matrix.By water and diammonium hydrogen citrate with mass ratio 100：2 ratio mixing, stirs into uniform mixed liquor, into mixed liquor
Soluble copper salt cupric pyrophosphate is added and sodium pyrophosphate stirring is configured to cupric electrodeposit liquid, wherein：Copper in cupric electrodeposit liquid
Ion concentration is 0.4mol/L；The concentration of acid ion pyrophosphate is 0.8mol/L in cupric electrodeposit liquid.By gained surface
The tabula rasa Copper substrate of polylactic acid microsphere template is covered with as working electrode, using platinum as to electrode, using calomel electrode as ginseng
Than electrode, prepared cupric electrodeposit liquid carries out electro-deposition as the solution system of electro-deposition, controls electro-deposition current density
For 7.5mAcm-2, control electrodeposition time is 500s, and it is micro- to remove polylactic acid in a manner of dissolution or calcination after electro-deposition
Composite construction copper is obtained after ball.Acid mixed solution is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：The sulfuric acid rubs
Your concentration is 0.5mol/L；The molar concentration of the ammonium chloride is 1mol/L；Potassium platinate and chlorine is added in oxytropism mixed liquor again
Change nickel, be configured to platinum electrodeposition of nickel liquid, in platinum electrodeposition of nickel liquid：The platinum ion molar concentration that the potassium platinate introduces is
0.05mol/L；The nickel ion molar concentration that the nickel chloride introduces is 0.2mol/L；Using composite construction copper obtained as work
Electrode, using platinum as to electrode, resulting platinum electrodeposition of nickel liquid carries out electro-deposition as the solution system of electro-deposition, it is heavy to control electricity
Product voltage is -1.2V, and current density is -400A/m2, sedimentation time 100s, dries after washing in 60 DEG C, obtains band after magnetization
The composite construction copper of magnetic-particle, i.e., magnetic lithium metal battery copper magnetic combination electrode material；By 1,3-dioxolane and 1,2- bis-
Ethyl Methyl Ether is with volume ratio 1：1 volume ratio is configured to base fluid, will be bis- (trifyl) imine lithium be dissolved in base fluid and making
At electrolyte, in electrolyte：The molar concentration of bis- (trifyl) imine lithiums is 1mol/L；With prepared electrolyte,
Obtained magnetic lithium metal battery copper magnetic combination electrode material and polypropylene diaphragm are material in the glove box equipped with argon gas
CR2025 button cell is assembled into get the magnetic lithium metal battery is arrived.Above-mentioned battery is subjected to electro-chemical test discovery,
Under 1mA/cm2 current density, without dendritic growth in 300 circles, coulombic efficiency is up to 98.2%.Its discharge procedure mechanism figure such as Fig. 2
It is shown.
Embodiment 6
Acid mixed solution is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：The molar concentration of the sulfuric acid is 0.8mol/
L；The molar concentration of the ammonium chloride is 2mol/L；Chloroplatinic acid is added in oxytropism mixed liquor again and is configured to platinum deposition liquid, platinum
In electrodeposit liquid：The platinum ion molar concentration that the chloroplatinic acid introduces is 0.1mol/L；By composite junction obtained in embodiment 1
Structure copper is as working electrode, and using graphite as to electrode, resulting platinum electrodeposit liquid carries out electricity as the solution system of electro-deposition
Deposition, control electro-deposition voltage are -2.4V, and current density is -200A/m2, sedimentation time 100s, are dried after washing in 60 DEG C
It is dry, the copper magnetic combination electrode material of carrying magnetic particle is obtained after magnetization, i.e., magnetic lithium metal battery copper magnetic combination electrode material.Again
By above-mentioned electrode material according in embodiment 1 assemble battery carry out electro-chemical test, 100 enclose in its coulombic efficiency up to 96% with
On.
Embodiment 7
It aluminizes first on Copper substrate surface, for aluminium coat with a thickness of 3mm, the method for recycling anodic oxidation prepares porous anode
Aluminium (AAO) template prepares copper nano-wire through AC electrodeposition using AAO template.The first step：AAO template is put into wt% by reaming
For in 5% phosphoric acid, 50 DEG C of constant temperature, 10min, then cleaned with distilled water.Second step：Electrolyte first matches the copper sulphate of 12.5g
It is dissolved in l00ml distilled water, magnetic agitation is to being completely dissolved, then molten 39g boric acid obtains CuS0 until being completely dissolved4Mixing electrolysis
Liquid.Third step：Acid copper nano wire.Copper nano-wire is prepared using AC electrodeposition.With the AAO after reaming for an electrode, carbon
Stick prepares copper nano-wire to electrode deposition.Acid mixed solution is then prepared with sulfuric acid, ammonium chloride and water again, in acid mixed solution：
The molar concentration of the sulfuric acid is 1mol/L；The molar concentration of the ammonium chloride is 1.3mol/L；Add in oxytropism mixed liquor again
Enter sodium nitrate and be configured to nickel deposition liquid, in electrodeposition of nickel liquid：The nickel ion molar concentration that the nickel nitrate introduces is 0.5mol/L；
Surface is prepared with the Copper substrate of copper nano-wire structure as working electrode, using platinum as to electrode, resulting electrodeposition of nickel liquid
Solution system as electro-deposition carries out electro-deposition, and control electro-deposition voltage is -3V, and current density is -400A/m2, when deposition
Between be 200s, dried after washing in 60 DEG C, the copper magnetic combination electrode material of carrying magnetic particle obtained after magnetization, i.e., magnetic lithium metal
Battery copper magnetic combination electrode material.Again by above-mentioned electrode material according in embodiment 1 assemble battery carry out electro-chemical test, 100
Its coulombic efficiency is up to 92% or more in enclosing.
Embodiment 8
So that copper-based matter is generated the nano wire or nanometer sheet of Kocide SD by impregnating in alkaline solution, then passes through magnetic agitation
NaOH (125mmol) is dissolved in deionized water (100mL), NaCl (34.2mmol) then is added, Na2S2O8(3.5mmol) and
CuSO4·5H2O(0.04mmol).Container containing prepared solution is maintained in 86 DEG C of water-bath, surface growth is had
Nano wire or the copper sheet of nanometer chip architecture immerse in solution 8 minutes to grow CuO NRA.Then copper sheet is taken out simultaneously from solution
It is rinsed with deionized water, is then dried in air.At under the conditions of finally placing it in 450 DEG C, H2It anneals 240 points in atmosphere
Clock obtains the composite construction copper that surface growth has Nanometer Copper band to restore CuO.Acidic mixed is prepared with sulfuric acid, ammonium chloride and water
Liquid, in acid mixed solution：The molar concentration of the sulfuric acid is 0.5mol/L；The molar concentration of the ammonium chloride is 1mol/L；Again
Sodium platinate and nickel chloride are added in oxytropism mixed liquor, is configured to platinum electrodeposition of nickel liquid, in platinum electrodeposition of nickel liquid：The sodium platinate
The platinum ion molar concentration of introducing is 0.05mol/L；The nickel ion molar concentration that the nickel chloride introduces is 0.2mol/L；It will system
The composite construction copper obtained is as working electrode, using platinum as to electrode, solution of the resulting platinum electrodeposition of nickel liquid as electro-deposition
System carries out electro-deposition, and control electro-deposition voltage is -1.2V, and current density is -300A/m2, sedimentation time 60s, after washing
It is dried in 60 DEG C, magnetic lithium metal battery copper magnetic combination electrode material is obtained after magnetization.Again by above-mentioned electrode material according to implementation
Battery is assembled in example 1 and carries out electro-chemical test, and 150 enclose its interior coulombic efficiency up to 97.6% or more.
Embodiment 9
Prepare the K of 0.1M2S2O8With the KOH solution of 3M, after copper sheet is impregnated the 200s time under 60 DEG C of water bath conditions, take out clear
It washes, then is placed in 180 DEG C of baking ovens and keeps the temperature 2h, make Cu (OH)2Dehydration, can be obtained the Cu/CuO composite wood of three-dimensional manometer cable architecture
Material.By using Na2SO4(1M) the electrochemical reduction CuO nano wire in three-electrode system is prepared on copper-based bottom as electrolyte
Cu nano wire.Obtain three-dimensional manometer line composite construction copper.Acid mixed solution, acidic mixed are prepared with sulfuric acid, ammonium chloride and water
In liquid：The molar concentration of the sulfuric acid is 0.5mol/L；The molar concentration of the ammonium chloride is 1mol/L；Oxytropism mixed liquor again
Middle addition potassium platinate and nickel chloride, are configured to platinum electrodeposition of nickel liquid, in platinum electrodeposition of nickel liquid：The platinum ion that the potassium platinate introduces
Molar concentration is 0.05mol/L；The nickel ion molar concentration that the nickel chloride introduces is 0.2mol/L；By copper current collector obtained
As working electrode, using platinum as to electrode, resulting platinum electrodeposition of nickel liquid carries out electro-deposition as the solution system of electro-deposition,
Control electro-deposition voltage is -1.2V, and current density is -300A/m2, sedimentation time 60s, is dried after washing in 60 DEG C, magnetization
The nano wire copper current collector of carrying magnetic particle is obtained afterwards.It is again that above-mentioned electrode material is electric according to battery progress is assembled in embodiment 1
Test chemical, 200 enclose its interior coulombic efficiency up to 91.5% or more.The present embodiment scanning electron microscope (SEM) photograph is as shown in Figure 5.
Embodiment 10
By copper magnetic composite material obtained in embodiment 1 according to assembling battery in embodiment 1.And battery is placed in 250mT's
Electro-chemical test is carried out in magnetic field, 200, which enclose its interior coulombic efficiency, is up to 95%.
Embodiment 11
Acid mixed solution is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：The molar concentration of the sulfuric acid is 0.1mol/
L；The molar concentration of the ammonium chloride is 0.75mol/L；Soluble metal compound is added in oxytropism mixed liquor again, is configured to
Electrodeposit liquid：Wherein, soluble metal compound be sodium platinate, nickel chloride and cobalt chloride, and sodium platinate introduce platinum ion
Concentration is 0.2mol/L, and the introduced chlorine ion concentration of nickel chloride is 2.0mol/L, and the introduced concentration of cobalt ions of cobalt chloride is
0.3mol/L；Again using Copper substrate as working electrode, using platinum or graphite as to electrode, using electrodeposit liquid as the molten of electro-deposition
Liquid system carries out electro-deposition, and control electro-deposition voltage is -0.1V, and current density is -100A/m2, sedimentation time 300s, washing
It is dried afterwards in 40 DEG C, Copper substrate of the surface with magnetic coating structure is obtained after magnetization to get multiple to magnetic lithium metal battery copper magnetic
Composite electrode material.
Embodiment 12
Acid mixed solution is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：The molar concentration of the sulfuric acid is 2mol/L；
The molar concentration of the ammonium chloride is 7.5mol/L；Soluble metal compound is added in oxytropism mixed liquor again, is configured to electricity
Deposit liquid：Wherein, soluble metal compound is sodium platinate, nickel chloride and cobalt chloride, and the platinum ion that sodium platinate introduces is dense
Degree is 0.2mol/L, and the introduced chlorine ion concentration of nickel chloride is 2.0mol/L, and the introduced concentration of cobalt ions of cobalt chloride is
0.3mol/L；Again using Copper substrate as working electrode, using platinum or graphite as to electrode, using electrodeposit liquid as the molten of electro-deposition
Liquid system carries out electro-deposition, and control electro-deposition voltage is -2.0V, and current density is -500A/m2, sedimentation time 10s, washing
It is dried afterwards in 150 DEG C, Copper substrate of the surface with magnetic coating structure is obtained after magnetization to get multiple to magnetic lithium metal battery copper magnetic
Composite electrode material.
Embodiment 13
The nickel sulfate solution of preparation 1mol/L, the formaldehyde of 0.1mol/L, the disodium ethylene diamine tetra-acetic acid solution of 0.05mol/L, and
PH to 12 is adjusted with sodium hydroxide.The copper sheet of diameter 15mm, thickness 0.1mm are placed in in above-mentioned plating solution, the electroless copper time
For 40s.Copper substrate of the surface with magnetic coating structure, and magnetic lithium metal battery copper magnetic will be obtained after the magnetization of above-mentioned nickel coating again
Combination electrode material carries out electro-chemical test according to battery is assembled in embodiment 1, and 80 enclose its interior coulombic efficiency up to 92%.
Embodiment 14
Electroplate liquid is prepared, electroplate liquid each component is respectively：NiSO4·6H2O, 60g/250mL；NiCl2·6H2O, 25g/250mL；
Boric acid, 7.5g/250mL；Citric acid, 2.5g/250mL.The oxide on Copper substrate surface is removed, then cleans, is dry, cleaning
Copper as matrix, using activated carbon electrodes as anode, using electroplate liquid as the solution system of electro-deposition carry out electro-deposition.Electricity is heavy
Product condition be：Electrodeposition time 15min, current density 40mA/cm-2, temperature is 20 DEG C.Magnetic is carried out to it after electro-deposition
Change, obtains the composite construction copper that surface has magnetic micro-nano structure, i.e., magnetic lithium metal battery copper magnetic combination electrode material.According to
Battery is assembled in embodiment 1 and carries out electro-chemical test, and 80 enclose its interior coulombic efficiency up to 94%.Its scanning electron microscope (SEM) photograph such as Fig. 7 institute
Show.
Embodiment 15
Electroplate liquid is prepared, electroplate liquid each component is respectively：NiSO4·6H2O, 60g/250mL；NiCl2·6H2O, 25g/250mL；
Boric acid, 7.5g/250mL；Citric acid, 2.5g/250mL.The oxide on Copper substrate surface is removed, then cleans, is dry, cleaning
Copper as matrix, using activated carbon electrodes as anode, using electroplate liquid as the solution system of electro-deposition carry out electro-deposition.Electricity is heavy
Product condition be：Electrodeposition time 10min, current density 20mA/cm-2, temperature is 15 DEG C.Magnetic is carried out to it after electro-deposition
Change, obtains the composite construction copper that surface has magnetic micro-nano structure, i.e., magnetic lithium metal battery copper magnetic combination electrode material.According to
Battery is assembled in embodiment 1 and carries out electro-chemical test, and 80 enclose its interior coulombic efficiency up to 89%.
Embodiment 16
Electroplate liquid is prepared, electroplate liquid each component is respectively：NiSO4·6H2O, 60g/250mL；NiCl2·6H2O, 25g/250mL；
Boric acid, 7.5g/250mL；Citric acid, 2.5g/250mL.The oxide on Copper substrate surface is removed, then cleans, is dry, cleaning
Copper as matrix, using activated carbon electrodes as anode, using electroplate liquid as the solution system of electro-deposition carry out electro-deposition.Electricity is heavy
Product condition be：Electrodeposition time 20min, current density 60mA/cm-2, temperature is 35 DEG C.Magnetic is carried out to it after electro-deposition
Change, obtains the composite construction copper that surface has magnetic micro-nano structure, i.e., magnetic lithium metal battery copper magnetic combination electrode material.According to
Battery is assembled in embodiment 1 and carries out electro-chemical test, and 80 enclose its interior coulombic efficiency up to 91%.
Embodiment 17
Acid mixed solution is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：The molar concentration of the sulfuric acid is 0.8mol/
L；The molar concentration of the ammonium chloride is 2mol/L；Chloroplatinic acid is added in oxytropism mixed liquor again and is configured to platinum deposition liquid, platinum
In electrodeposit liquid：The platinum ion molar concentration that the chloroplatinic acid introduces is 0.1mol/L；By surface obtained in embodiment 14
Composite construction copper with magnetic micro-nano structure is as working electrode, and using graphite as to electrode, resulting platinum electrodeposit liquid is made
Electro-deposition is carried out for the solution system of electro-deposition, control electro-deposition voltage is -2.4V, and current density is -200A/m2, when deposition
Between be 100s, dried after washing in 60 DEG C, obtain the magnetic coupling structure that surface has magnetic micro-nano structure doped magnetic particle
Copper, i.e., magnetic lithium metal battery copper magnetic combination electrode material.Above-mentioned electrode material is carried out according to assembly battery in embodiment 1 again
Electro-chemical test, 100 enclose its interior coulombic efficiency up to 96% or more.The present embodiment scanning electron microscope (SEM) photograph is as shown in Figure 6.
Embodiment 18
Acid mixed solution is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：The molar concentration of the sulfuric acid is 0.8mol/
L；The molar concentration of the ammonium chloride is 2mol/L；Nickel chloride, cobalt chloride and iron chloride are added in oxytropism mixed liquor again to prepare
At meeting electrodeposit liquid, in composite electrodeposition liquid：The nickel ion molar concentration that the nickel chloride introduces is 3.0mol/L, the chlorine
Changing the introduced cobalt ions molar concentration of cobalt is 0.05mol/L, and the introduced iron ion molar concentration of the iron chloride is
0.2mol/L；Have the composite construction copper of magnetic micro-nano structure as working electrode on surface obtained in embodiment 14, with stone
For ink as to electrode, resulting platinum electrodeposit liquid carries out electro-deposition as the solution system of electro-deposition, control electro-deposition voltage for-
2.4V, current density are -200A/m2, sedimentation time 100s, are dried after washing in 60 DEG C, and obtaining surface has magnetic micro-nano
The magnetic coupling structure copper of structure doped magnetic particle, i.e., magnetic lithium metal battery copper magnetic combination electrode material.Again by above-mentioned electricity
Pole material carries out electro-chemical test according to battery is assembled in embodiment 1, and 100 enclose its interior coulombic efficiency up to 96% or more.
Claims (10)
1. a kind of preparation process of magnetism lithium metal battery copper magnetic combination electrode material, which is characterized in that the preparation process packet
Include following preparation step：
1) then the oxide for removing Copper substrate surface cleans, is dry；
2) magneto spheric structure containing magnetic metal is prepared on the Copper substrate surface handled through step 1)；
Wherein, the magnetic metal includes iron, cobalt, nickel and platinum, and the magneto spheric structure includes magnetic coating structure, non magnetic micro-nano knot
Structure doped magnetic particle, magnetic micro-nano structure doped magnetic particle and magnetic micro-nano structure.
2. a kind of preparation process of magnetic lithium metal battery copper magnetic combination electrode material according to claim 1, feature
It is, the preparation process of the magnetic coating structure includes following preparation step：
A1 acid mixed solution) is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：
The molar concentration of the sulfuric acid is 0.1~2mol/L；
The molar concentration of the ammonium chloride is 0.75~7.5mol/L；
Soluble metal compound is added in oxytropism mixed liquor again, is configured to electrodeposit liquid：
Wherein, soluble metal compound is soluble magnetic metal compound, and it meets following conditions：
The magnetic metal ion molar concentration that the solubility magnetic metal compound introduces is 0.2~2.0mol/L；
A2 made with step A1) using platinum or graphite as to electrode) using Copper substrate obtained by step 1) as working electrode
The electrodeposit liquid obtained carries out electro-deposition as the solution system of electro-deposition, and control electro-deposition voltage is -0.1~-2.0V, and electric current is close
Degree is -100~-500A/m2, sedimentation time is 10~300s, is dried after washing in 40~150 DEG C, obtains surface and plates with magnetic
The Copper substrate of layer structure is to get to magnetic lithium metal battery copper magnetic combination electrode material.
3. a kind of preparation process of magnetic lithium metal battery copper magnetic combination electrode material according to claim 1, feature
It is, described the step of preparing non magnetic micro-nano structure doped magnetic particle includes：
B1 copper micro-nano structure) is prepared on the Copper substrate surface handled through step 1), obtains composite construction Copper substrate；
B2 acid mixed solution) is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：
The molar concentration of the sulfuric acid is 0.1~2mol/L；
The molar concentration of the ammonium chloride is 0.75~7.5mol/L；
Soluble magnetic metal compound is added in oxytropism mixed liquor again, is configured to the electrodeposit liquid of the ingredient containing magnetic metal,
In the electrodeposit liquid of the ingredient containing magnetic metal：
The magnetic metal ion molar concentration that the solubility magnetic metal compound introduces is 0.05~4.0mol/L；
B3) using composite construction Copper substrate obtained by step B1) as working electrode, using platinum or graphite as to electrode, with step
Rapid B2) obtained by the electrodeposit liquid of the ingredient containing magnetic metal carry out electro-deposition as the solution system of electro-deposition, it is heavy to control electricity
Product voltage is -0.1~-2.0V, and current density is -100~-500A/m2, sedimentation time is 10~300s, after washing in 40~
150 DEG C of drying obtain Copper substrate of the surface with non magnetic micro-nano structure doped magnetic particle to get magnetic lithium metal battery is arrived
Copper magnetic combination electrode material.
4. a kind of preparation process of magnetic lithium metal battery copper magnetic combination electrode material according to claim 1, feature
It is, the step of preparation magnetic micro-nano structure doped magnetic particle includes：
C1 magnetic micro-nano structure) is prepared on the Copper substrate surface handled through step 1), obtains magnetic coupling structure Copper substrate, wherein
Magnetic micro-nano structure is the micro-nano structure of the ingredient containing magnetic metal；
C2 acid mixed solution) is prepared with sulfuric acid, ammonium chloride and water, in acid mixed solution：
The molar concentration of the sulfuric acid is 0.1~2mol/L；
The molar concentration of the ammonium chloride is 0.75~7.5mol/L；
Soluble magnetic metal compound is added in oxytropism mixed liquor again, is configured to the electrodeposit liquid of the ingredient containing magnetic metal,
In the electrodeposit liquid of the ingredient containing magnetic metal：
The magnetic metal ion molar concentration that the solubility magnetic metal compound introduces is 0.05~4.0mol/L；
C3) using magnetic coupling structure Copper substrate obtained by step C1) as working electrode, using platinum or graphite as to electrode,
Electro-deposition, control are carried out using the electrodeposit liquid of the ingredient containing magnetic metal obtained by step C2) as the solution system of electro-deposition
Electro-deposition voltage is -0.1~-2.0V, and current density is -100~-500A/m2, sedimentation time be 10~300s, after washing in
40~150 DEG C of drying, obtaining surface has the Copper substrate of magnetic micro-nano structure doped magnetic particle to get magnetic lithium metal electricity is arrived
Pond copper magnetic combination electrode material.
5. a kind of preparation process of magnetic lithium metal battery copper magnetic combination electrode material according to claim 1, feature
It is, the step of preparation magnetic micro-nano structure includes：
D1) in the micro-nano structure of the Copper substrate surface preparation ingredient containing magnetic metal handled through step 1), in 40~150 after washing
DEG C drying, obtaining surface has the Copper substrate of magnetic micro-nano structure to get to magnetic lithium metal battery copper magnetic combination electrode material.
6. a kind of preparation work of magnetism lithium metal battery copper magnetic combination electrode material according to Claims 2 or 3 or 4 or 5
Skill, which is characterized in that step A2), step B3) and step C3) electrodeposition process control electro-deposition voltage is -0.1~-
1.2V, current density are -200~-400A/m2, sedimentation time is 60s~100s.
7. a kind of magnetic lithium metal battery copper magnetic composite material prepared by claims 1 or 2 or 3 or 4 or 5 techniques,
It is characterized in that, the copper magnetic composite material prepares the magnetosphere knot containing magnetic metal on Copper substrate surface using copper as matrix
Structure, the magnetic metal include iron, cobalt, nickel and platinum.
8. a kind of magnetic lithium metal battery copper magnetic composite material according to claim 7, which is characterized in that the magnetosphere knot
Structure includes that magnetic coating structure, non magnetic micro-nano structure doped magnetic particle, magnetic micro-nano structure doped magnetic particle and magnetism are micro-
Micro-nano structure.
9. a kind of magnetic lithium metal battery comprising the copper magnetic composite material as described in claim 7 or 8, which is characterized in that described
The negative electrode material of magnetic lithium metal battery is copper magnetic composite material, using bis- (trifyl) imine lithium solution as electrolysis
Matter, using high molecular material as diaphragm.
10. a kind of magnetic lithium metal battery according to claim 9, which is characterized in that bis- (fluoroforms in the electrolyte
Sulfonyl) imine lithium molar concentration be 0.5~2mol/L, the diaphragm be polypropylene diaphragm.
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| CN114226436A (en) * | 2021-11-30 | 2022-03-25 | 浙江大学杭州国际科创中心 | Metal nanocrystalline modified composite electrode and preparation method and application thereof |
| CN114300688A (en) * | 2021-12-28 | 2022-04-08 | 上海恩捷新材料科技有限公司 | Battery containing magnetic current collector and preparation method thereof |
| CN115044814A (en) * | 2022-05-20 | 2022-09-13 | 同济大学 | Magnetic metal-based composite material and preparation method and application thereof |
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| CN101809206A (en) * | 2007-09-28 | 2010-08-18 | 日矿金属株式会社 | Copper foil for printed circuit and copper clad laminate |
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| CN112713260A (en) * | 2019-10-25 | 2021-04-27 | 广州汽车集团股份有限公司 | Flexible lithium metal battery cathode, preparation method thereof and lithium metal battery |
| CN112713260B (en) * | 2019-10-25 | 2022-12-23 | 广州汽车集团股份有限公司 | Flexible lithium metal battery cathode, preparation method thereof and lithium metal battery |
| CN114226436A (en) * | 2021-11-30 | 2022-03-25 | 浙江大学杭州国际科创中心 | Metal nanocrystalline modified composite electrode and preparation method and application thereof |
| CN114300688A (en) * | 2021-12-28 | 2022-04-08 | 上海恩捷新材料科技有限公司 | Battery containing magnetic current collector and preparation method thereof |
| CN114300688B (en) * | 2021-12-28 | 2024-01-16 | 上海恩捷新材料科技有限公司 | Battery containing magnetic current collector and preparation method thereof |
| CN115044814A (en) * | 2022-05-20 | 2022-09-13 | 同济大学 | Magnetic metal-based composite material and preparation method and application thereof |
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