CN109802121A

CN109802121A - Carbon material, preparation method and application containing metal coating

Info

Publication number: CN109802121A
Application number: CN201910072986.6A
Authority: CN
Inventors: 郑子剑; 常建; 高源�
Original assignee: Hong Kong Polytechnic University HKPU
Current assignee: Hong Kong Polytechnic University HKPU
Priority date: 2019-01-25
Filing date: 2019-01-25
Publication date: 2019-05-24

Abstract

The present invention provides a kind of carbon material containing metal coating, preparation method and applications, the preparation method comprises the following steps: A) carbon material is subjected to surface oxidation in acid solution, then it is mixed with catalyst solution, obtains the carbon material of catalyst supported on surface；B) carbon material of the catalyst supported on surface is waited for depositing in plating solution in metal, obtains the carbon material containing metal coating.Quick humidification and the diffusion of lithium may be implemented according to the carbon material containing metal coating that above scheme is prepared.It can guarantee that lithium metal battery has preferably cyclical stability by the lithium metal battery negative electrode material that this carbon material containing metal coating is prepared.In addition, showing excellent mechanical stability in bending process repeatedly by the lithium metal battery negative electrode material that this carbon material containing metal coating is prepared.

Description

Carbon material, preparation method and application containing metal coating

Technical field

The present invention relates to technical field of fibre production more particularly to a kind of carbon materials containing metal coating, its preparation side Method and application.

Background technique

With wearable electronic, intelligent clothing, electronic skin, flexible smart phone, folding display and can The rapid development of implantable medical devices, conventional lithium ion battery are unable to satisfy flexibility and want because its volume is larger, rigidity is relatively strong It asks.

For the wearable device of continued power, the light flexible storage with high-energy density and electrochemical stability Energy unit is necessary.Although having there is many researchs to improve lithium ion about by structure interconnection or design of material The flex capability of battery, but used intercalation electrode has reached the limit of theoretical specific capacity.

In all materials that can be used for electrode of lithium cell, lithium metal is because of its higher theoretical specific capacity (3860mAh/g) With lower electrochemical potentials (- 3.04V, relative to standard hydrogen electrode), the lithium battery made energy density with higher, Thus, lithium metal is optimal anode.Although bare lithium foil electrode has above advantages, however, in bending repeatedly In the process, the resistance of bare lithium foil electrode can continue to increase, or even ductile fracture occur.Furthermore lithium foil in cyclic process Dendritic growth and biggish volume change will lead to coulombic efficiency reduction, irreversible capacitance loss, electrolyte quickly dry up Even internal short-circuit, further hinders its application in flexible energy storage material.

The prior art reports some methods that can stablize conventional lithium metal anode, the solid electrolytic including engineer Matter interface (SEI) uses electrolyte additive and the load lithium substrate of the high surface area of exploitation.However, first two method can not Solve the mechanical stability of lithium anodes.Therefore, there is the such as oxygen-enriched graphene film of various Flexible Electrophilic stone substrates, nickel Nano wire paper, silver or silicon coating paper, polyimides (PI) carbon paper containing Zinc oxide coating are by hot submersion method for storing lithium. Compared with plating, hot submersion method has the advantages that simple, reliable, high production efficiency and lithium are evenly distributed by absorbing molten lithium. However, wetting and diffusion of the liquid lithium on above-mentioned substrate are slower, it is not suitable for actual large-scale production.For example, in flexibility Or array printing liquid lithium requires the uniform of high humidity lubricant nature, quick diffusion velocity and any scale of lithium metal on the substrate of rigidity Property.Furthermore oxygen-containing functional group impurity or lithium alloy that fusion process introduces cause the coulombic efficiency of lithium metal battery and circulation steady It is qualitative poor.Therefore, while the mechanical stability of lithium anode is realized and chemical stability is still a huge challenge.

Summary of the invention

In view of this, the technical problem to be solved in the present invention is that providing a kind of carbon material containing metal coating, its system Preparation Method and application, the carbon material prepared by the present invention containing metal coating may be implemented quick humidification and the diffusion of lithium, obtain Lithium metal battery negative electrode material can guarantee that lithium metal battery has preferably cyclical stability.

The present invention provides a kind of preparation methods of carbon material containing metal coating, comprising the following steps:

A) carbon material is carried out in acid solution to surface oxidation, then mixed with catalyst solution, area load is obtained and urges The carbon material of agent；

B) carbon material of the catalyst supported on surface is waited for depositing in plating solution in metal, is obtained containing metal coating Carbon material.

Preferably, the carbon material includes carbon fiber, carbon line, braiding carbon cloth, on-woven carbon cloth, carbon paper or carbon felt.

Preferably, step A) in, carbon material is subjected to surface oxidation in acid solution specifically: it is molten that carbon material is immersed acid In liquid, at 25~60 DEG C, it is ultrasonically treated 5~60min；Or by carbon material immerse acid solution in, at 25~60 DEG C, oxygen etc. from 5~60min of subprocessing；

The acid solution includes sulfuric acid solution and nitric acid solution, and the volume ratio of the sulfuric acid solution and nitric acid solution is 3:1；

The catalyst solution is the aqueous solution of ammonium chloropalladate, and the concentration of the aqueous solution of the ammonium chloropalladate is 1 × 10^-4~ 5×10^-3mol/L；

Described mix with catalyst solution carries out in dark conditions, and the mixed time is 10~20min.

Preferably, step A) in, after the surface oxidation further include:

Carbon material after the surface oxidation is subjected to silanization treatment, then is immersed containing [2- (methacryloxy) Ethyl] trimethyl ammonium chloride and potassium peroxydisulfate mixed solution in, the carbon of the coating containing PMETAC is obtained after Raolical polymerizable Material.

Preferably, the reagent that the silanization treatment uses is the alcoholic solution of vinyl trimethoxy siloxanes；

In the alcoholic solution of the vinyl trimethoxy siloxanes, the volumn concentration of vinyl trimethoxy siloxanes It is 5~20%；

The time of the silanization treatment is 0.5~1.0h；

In mixed solution containing [2- (methacryloxy) ethyl] trimethyl ammonium chloride and potassium peroxydisulfate, [2- (first Base acryloxy) ethyl] trimethyl ammonium chloride concentration be 5~30wt%；The concentration of potassium peroxydisulfate is 0.1~0.5wt%；

The temperature of the Raolical polymerizable is 80~120 DEG C, time of the Raolical polymerizable is 0.5~ 2.0h。

Preferably, step B) in, the metal in the metal coating includes copper, nickel, silver, zinc, aluminium or manganese.

The present invention also provides a kind of carbon materials containing metal coating of preparation method preparation described above.

The present invention also provides a kind of preparation methods of lithium metal battery negative electrode material, comprising the following steps:

The hot melt absorption that the carbon material containing metal coating is carried out to lithium at 350~400 DEG C, obtains lithium metal electricity Pond negative electrode material；

The carbon material containing metal coating is the carbon material described above containing metal coating.

Preferably, before the hot melt absorption further include:

The carbon material containing metal coating is subjected to oxidation processes；

The temperature of the oxidation processes is 25~300 DEG C, and the time of the oxidation processes is 0.1~6.0h.

The present invention also provides a kind of lithium metal battery negative electrode materials of preparation method preparation described above.

The present invention also provides a kind of lithium metal battery, including anode, cathode, diaphragm and electrolyte, the cathode includes Lithium metal battery negative electrode material described above.

The present invention provides a kind of preparation methods of carbon material containing metal coating, comprising the following steps: A) by carbon materials Material carries out surface oxidation in acid solution, then mixes with catalyst solution, obtains the carbon material of catalyst supported on surface；B) will The carbon material of the catalyst supported on surface waits for being deposited in plating solution in metal, obtains the carbon material containing metal coating.It presses Quick humidification and the diffusion of lithium may be implemented according to the carbon material containing metal coating that above scheme is prepared.By it is this containing The lithium metal battery negative electrode material that the carbon material of metal coating is prepared can guarantee that lithium metal battery has and preferably recycle Stability.In addition, the lithium metal battery negative electrode material being prepared by this carbon material containing metal coating is curved repeatedly Excellent mechanical stability is shown during bent.

The experimental results showed that contact angle of the lithium drop on the carbon material containing metal coating that the present invention is prepared is 0 °, surface wettability is very excellent.Also, impregnating speed of the lithium drop on the carbon material containing metal coating is very Fastly.At 350 DEG C, diffusion velocity range of the lithium drop on the carbon material containing metal coating is 0.01~3.0m min^-1.When Temperature further increases, and the diffusion velocity of lithium drop can further increase.

The lithium metal battery negative electrode material and LiFePO4 (LFP) be prepared by the above-mentioned carbon material containing metal coating After anode pairing, the full battery assembled has 8.0mA cm^-2High rate capability, in 1.0mA cm^-2Under conditions of, pass through After 500 circulations, coulombic efficiency is more stable close to 100%, still has preferably cyclical stability.

Detailed description of the invention

Fig. 1, which is negative, is loaded with the braiding carbon cloth chemical deposition metallic copper of the coating containing PMETAC of chlorine palladium acid group, then carries out lithium Hot melt absorption procedure chart；

Fig. 2 is contact angle of the lithium drop on different matrix surface；

Fig. 3 is the XRD diagram of CFCu and CF；

Fig. 4 is the LMM energy spectrum diagram of CuXPS in the CFCu of embodiment 1；

Fig. 5 is that diffusion velocity of the lithium drop on the CFCu of embodiment 1 compares bar chart；

The SEM figure that Fig. 6 is CFCu prepared by the embodiment of the present invention 1 and CFCu-Li；

Fig. 7 is the symmetrical half-cell that is assembled into of CFCu-Li in 1.0mA cm^-2Under plating/strip cycles Capacity Plan；

Fig. 8 is the symmetrical half-cell that is assembled into of CFCu-Li in constant current 2.0mA cm^-2Under circulation volume figure；

The SEM figure that Fig. 9 is CFCu-Li prepared by embodiment 1；

Figure 10 is the XRD diagram of the CFCu and CFCu-Li in embodiment 1；

Figure 11 is the surface resistance variation diagram of CFCu-Li continuous bend under differently curved radius；

Figure 12 is the high rate performance curve of lithium metal battery prepared by embodiment 1；

Figure 13 is the first charge-discharge curve for the lithium metal battery that CFCu-Li prepared by embodiment 1 is cathode；

Figure 14 is the cycle performance curve and coulombic efficiency curve of lithium metal battery prepared by embodiment 1；

Figure 15 is the digital picture of lithium metal lithium wicking process on the CYCu of embodiment 5 of liquid；

Figure 16 be in embodiment 5 the symmetrical half-cell that is assembled into of CYCu-Li in 0.1mA cm^-2Under plating/strip cycles Capacity Plan；

Figure 17 is the charging and discharging curve for the lithium metal battery that CYCu-Li prepared by embodiment 5 is cathode；

Figure 18 is the cycle performance curve and coulombic efficiency curve of lithium metal battery prepared by embodiment 5.

Specific embodiment

Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair The range of bright protection.

Carbon material is first carried out surface oxidation by the present invention in acid solution.In the embodiment of the present invention, the carbon material packet Include carbon fiber, carbon line, braiding carbon cloth, on-woven carbon cloth, carbon paper or carbon felt.In an embodiment of the present invention, the acid solution packet Include sulfuric acid solution and nitric acid solution, the volume ratio of the sulfuric acid solution and nitric acid solution is 3:1.Acid solution can aoxidize above-mentioned carbon The surface of every fiber, allows fiber surface rich in oxygen-containing functional group in material.

In an embodiment of the present invention, carbon material is carried out to surface oxidation in acid solution specifically: immerse carbon material In acid solution, at 25~60 DEG C, it is ultrasonically treated 5~60min；Or immerse carbon material in acid solution, at 25~60 DEG C, oxygen 5~60min of plasma treatment.The ultrasonic treatment or oxygen plasma treatment can advantageously reduce oxidation with accelerated oxidation process Time.In certain embodiments, the temperature of the ultrasonic treatment is 60 DEG C or 25 DEG C, and the time of the ultrasonic treatment is 60min.

In certain embodiments of the present invention, after the surface oxidation further include:

In certain embodiments of the present invention, before the silanization treatment further include: by the carbon materials after the surface oxidation Material is washed and is dried.In certain embodiments, the washing, which is adopted, is washed with deionized.In certain embodiments, described Dry temperature is 25~100 DEG C.In certain embodiments, the temperature of the drying is 80 DEG C.In certain embodiments, described The dry time is 5~30min.In certain embodiments, the time of the drying is 10min.

In an embodiment of the present invention, the reagent that the silanization treatment uses is the alcohol of vinyl trimethoxy siloxanes Solution.In the alcoholic solution of the vinyl trimethoxy siloxanes, the volumn concentration of vinyl trimethoxy siloxanes is 5 ~20%.In certain embodiments, in the alcoholic solution of the vinyl trimethoxy siloxanes, vinyl trimethoxy siloxanes Volumn concentration be 10% or 15%.In certain embodiments, the time of the silanization treatment is 0.5~1.0h.? In some embodiments, the time of the silanization treatment is 1.0h or 0.5h.The silanization treatment can draw in fiber surface Enter functional group containing double bonds.

After silanization treatment, then immerse containing [2- (methacryloxy) ethyl] trimethyl ammonium chloride and potassium peroxydisulfate Mixed solution in, the carbon material of the coating containing PMETAC is obtained after Raolical polymerizable.The fiber surface of silanization is rich in double With [2- (methacryloxy) ethyl] trimethyl ammonium chloride containing double bonds free radical polymerization can occur for key functional group, this A process, which needs to polymerize, to be caused.Here potassium peroxydisulfate is exactly the initiator that free radical polymerization above needs.

In an embodiment of the present invention, contain [2- (methacryloxy) ethyl] trimethyl ammonium chloride and potassium peroxydisulfate Mixed solution in, the concentration of [2- (methacryloxy) ethyl] trimethyl ammonium chloride is 5~30wt%；Potassium peroxydisulfate Concentration is 0.1~0.5wt%, and solvent is water.In certain embodiments, described to contain [2- (methacryloxy) ethyl] three In the mixed solution of ammonio methacrylate and potassium peroxydisulfate, the concentration of [2- (methacryloxy) ethyl] trimethyl ammonium chloride is 20wt%；The concentration of potassium peroxydisulfate is 0.3wt%, and solvent is water.

In an embodiment of the present invention, the temperature of the Raolical polymerizable is 80~120 DEG C.In some embodiments In, the temperature of the Raolical polymerizable is 80 DEG C.In an embodiment of the present invention, the time of the Raolical polymerizable For 0.5~2.0h.In certain embodiments, the time of the Raolical polymerizable is 1.0h.

It in an embodiment of the present invention, can be directly molten with catalyst after carbon material carries out surface oxidation in acid solution Liquid mixing, obtains the carbon material of catalyst supported on surface.It is also possible to after carbon material carries out surface oxidation in acid solution, into Row silanization treatment, then to immerse the mixing containing [2- (methacryloxy) ethyl] trimethyl ammonium chloride and potassium peroxydisulfate molten The carbon material of the coating containing PMETAC is obtained in liquid, after Raolical polymerizable, then, then is mixed with catalyst solution, is obtained table The carbon material of face supported catalyst.The carbon material of the coating containing PMETAC can make the lithium metal battery negative electrode material finally obtained It is more flexible.It in an embodiment of the present invention, further include to coating containing PMETAC after the carbon material for obtaining the coating containing PMETAC Carbon material washed and dried.In certain embodiments, the washing, which is adopted, is washed with deionized.In some embodiments In, the temperature of the drying is 25~100 DEG C.In certain embodiments, the temperature of the drying is 80 DEG C.In some embodiments In, the time of the drying is 5~30min.In certain embodiments, the time of the drying is 10min.

In an embodiment of the present invention, the catalyst solution is the aqueous solution of ammonium chloropalladate.The water of the ammonium chloropalladate The concentration of solution is 1 × 10-⁴~5 × 10-³mol/L.In certain embodiments, the concentration of the aqueous solution of the ammonium chloropalladate is 5 ×10-³Mol/L or 3 × 10-³mol/L。

In certain embodiments of the present invention, described mix with catalyst solution carries out in dark conditions.It is described mixed The time of conjunction is 10~20min.In certain embodiments, the mixed time is 20min.The item for being blended in non-strong light It is carried out under part, catalyst can be further avoided and be reduced to metal under the irradiation of strong light, and lose catalytic activity.

After obtaining the carbon material of catalyst supported on surface, the carbon material of the catalyst supported on surface is waited for into plating solution in metal In deposited, obtain the carbon material containing metal coating.

In certain embodiments of the present invention, the metal waits for that plating solution includes the solution of metal ion.In the present invention Metal waits for that plating solution can be self-control, or it is commercially available, special limitation is had no to this.In certain embodiments, the metal It is the sulfate liquor of metal ion to plating solution, such as: copper-bath, nickel sulfate solution, silver sulfate solution, zinc sulfate are molten Liquid, aluminum sulfate solution or manganese sulfate solution.In certain embodiments of the present invention, the metal in the metal coating include copper, Nickel, silver, zinc, aluminium or manganese.In certain embodiments, the metal waits for that plating solution is copper plating bath, and the copper plating bath includes A liquid and B liquid, The A liquid be include NaOH (12g/L), CuSO₄The aqueous solution of (13g/L) and sodium potassium tartrate tetrahydrate (29g/L)；The B liquid is The aqueous solution (9.5mL/L) of HCHO；The volume ratio of the A liquid and B liquid is 1:1.In certain embodiments, the metal waits for plating solution For silver plating liquid, the silver plating liquid be include [Ag (NH₃)₂]NO₃The aqueous solution of (1g/L) and sodium potassium tartrate tetrahydrate (5g/L).Certain In embodiment, the metal waits for that plating solution is nickel-plating liquid, and the nickel-plating liquid includes a liquid and b liquid, a liquid be include Ni₂SO₄ The aqueous solution of (40g/L), sodium citrate (20g/L) and lactic acid (10g/L)；The b liquid is the water of dimethylamine borane (7.5g/L) Solution；The volume ratio of a liquid and b liquid is 10:1.

In an embodiment of the present invention, the deposition can be chemical deposition, or electrochemical deposition.In the present invention Embodiment in, time of the chemical deposition is 5~30min.In certain embodiments, the time of the chemical deposition is 10min.In an embodiment of the present invention, the time of the electrochemical deposition is 5~30min；It is described to be electrochemically-deposited in electric current For 0.5~2.0mA cm-²In the case where carry out.In certain embodiments, described to be electrochemically-deposited in 1.0mA cm-²It is constant It is carried out under electric current, the time of the electrochemical deposition is 10min.

Chlorine palladium acid group can become porpezite metal particles in a reducing environment, and there is catalysis to restore each metal ion species for they Effect, such as Cu²⁺By catalysis to quickly be reduced into Ni metal particle, the Ni metal particle being reduced here can be further Serve as new catalyst.In the embodiment of the present invention, metal waits for that plating solution can provide reducing environment, specific to some embodiments In, metal waits for that sodium potassium tartrate tetrahydrate, HCHO or dimethylamine borane in plating solution are reducing agent, provides reducing environment.

The present invention also provides a kind of carbon materials containing metal coating that preparation method described above is prepared.This hair Quick humidification and the diffusion of lithium may be implemented in the bright obtained carbon material containing metal coating.In an embodiment of the present invention, lithium Contact angle of the drop on the carbon material containing metal coating that the present invention is prepared is 0 °, and surface wettability is very excellent It is different.Also, impregnating speed of the lithium drop on the carbon material containing metal coating is very fast.At 300~400 DEG C, contain Lithium drop can be adsorbed by having the carbon material of metal coating.At 350 DEG C, lithium drop is on the carbon material containing metal coating Diffusion velocity range is 0.01~3.0m min^-1.When temperature further increases, the diffusion velocity of lithium drop can be further increased.

The hot melt absorption that carbon material described above containing metal coating is carried out to lithium at 350~400 DEG C, obtains lithium gold Belong to cell negative electrode material.

In an embodiment of the present invention, before hot melt absorption further include: by the carbon material containing metal coating into Row oxidation processes.

In certain embodiments, the oxidation processes are as follows: the carbon material containing metal coating is exposed in air. In certain embodiments, the temperature of the oxidation processes is the temperature of exposure, and the temperature of the oxidation processes is 25~300 DEG C. In certain embodiments, the temperature of the oxidation processes is 25 DEG C or 50 DEG C.In certain embodiments, the oxidation processes when Between be exposure time.In certain embodiments, the time of the oxidation processes is 0.1~6.0h.In certain embodiments, institute The time for stating oxidation processes is 6.0h.Carbon material containing metal coating is after oxidation processes, in the surface shape of metal coating The metal oxide layer for being 1.0~5.0nm at a layer thickness.

In an embodiment of the present invention, the lithium that the hot melt absorption of the lithium is used includes the lithium metal of liquid or the lithium of liquid Alloy.

In an embodiment of the present invention, the carbon material described above containing metal coating is subjected to lithium at 350~400 DEG C Hot melt absorption specifically: at 350~400 DEG C, the edge of the carbon material described above containing metal coating is exposed to lithium In liquid.The lithium liquid includes the lithium metal of liquid or the lithium alloy of liquid.

The temperature of the hot melt absorption of the lithium is 350~400 DEG C.In certain embodiments, the hot melt of the lithium adsorbs Temperature is 350 DEG C or 400 DEG C.The edge of carbon material described above containing metal coating is exposed in lithium liquid, lithium liquid can be fast The carbon material containing metal coating is infiltrated fastly, and quickly diffusion wherein.In an embodiment of the present invention, the hot melt of the lithium The time of absorption is 0.5~120s.In certain embodiments, the time of the hot melt absorption of the lithium is 0.6s.

In an embodiment of the present invention, the hot melt of the lithium is adsorbed on O₂And H₂The content of O lower than 1.0ppm environment in into Row.The hot melt of the lithium is adsorbed in argon filling glove box and carries out.

The present invention also provides a kind of lithium metal battery negative electrode materials of preparation method preparation described above.By this lithium The lithium metal battery of metal battery negative electrode material preparation has preferably cyclical stability.Meanwhile containing metal coating by this The lithium metal battery negative electrode material that is prepared of carbon material excellent mechanical stability is shown in bending process repeatedly.

In an embodiment of the present invention, it after lithium metal battery negative electrode material and LiFePO4 (LFP) anode match, is assembled Full battery have 8.0mA cm^-2High rate capability, in 1.0mA cm^-2Under conditions of, after 500 circulations, capacity is protected Holdup is not less than 95%, and coulombic efficiency is more stable close to 100%, thus, there is preferable cycle performance.

The present invention does not have special limitation to the type of the anode, diaphragm and electrolyte, e.g., with LiFePO4 (LFP) Or sulphur is anode, microporous barrier is diaphragm, and glycol dimethyl ether (DME) and 1,3-dioxolane (DOL) can be used in the electrolyte Mixed liquor.Then directly make specifically, above-mentioned lithium metal battery negative electrode material shear according to electrode size and shape For negative electrode tab, with LiFePO4 (LFP) for positive plate, according to electrode size (40 μ L cm^-2), DOL/DME (DME:DOL=1: 1 (V/V)) in be added contain 2wt%LiNO₃1mol/L LiTFSI electrolyte, obtain electrolyte, assembled in argon filling glove box At stainless steel coin battery and flexible-packed battery.

The present invention has no special limitation to the source of above-mentioned used raw material, can be general commercially available.

In an embodiment of the present invention, lithium drop connecing on the carbon material containing metal coating that the present invention is prepared Feeler is 0 °, and surface wettability is very excellent.Also, dipping speed of the lithium drop on the carbon material containing metal coating It spends very fast.At 300~400 DEG C, the carbon material containing metal coating can adsorb lithium drop.At 350 DEG C, lithium drop Diffusion velocity range on the carbon material containing metal coating is 0.01~3.0m min^-1.When temperature further increases, lithium liquid The diffusion velocity of drop can further increase.

It is in bending radius by the lithium metal battery negative electrode material that the above-mentioned carbon material containing metal coating is prepared Continuous bend is carried out under conditions of 5.0mm, can at least be born 1000 bendings and is then broken, it is steady to show excellent machinery It is qualitative.

The lithium metal battery negative electrode material and LiFePO4 (LFP) be prepared by the above-mentioned carbon material containing metal coating After anode pairing, the full battery assembled has 8.0mA cm^-2High rate capability；In 8.0mAcm^-2High current under still Higher output voltage and high-capacitance can be showed, show excellent fast charging and discharging performance.In 1.0mA cm^-2Item Under part, after 500 circulations, capacity retention ratio 95%, coulombic efficiency is more stable close to 100%.In 30 μ A cm^-1Item Under part, after cycle charge-discharge 400 times, capacity retention ratio 80%, coulombic efficiency is more stable close to 100%.Thus, have excellent Coulombic efficiency and cyclical stability.

In order to further illustrate the present invention, with reference to embodiments to a kind of carbon containing metal coating provided by the invention Material, preparation method and application are described in detail, but cannot be understood as limiting the scope of the present invention.

Carbon cloth specification is woven in embodiment:

Line density are as follows: direction of warp and weft is all 210 carbon lines of per inch, surface density: 6.0~12.0mg cm^-2, weave carbon cloth With a thickness of 100~200 μm.

Embodiment 1

The braiding carbon cloth is immersed in acid solution, at 60 DEG C, is ultrasonically treated 60min.The acid solution includes sulfuric acid The volume ratio of solution and nitric acid solution, the sulfuric acid solution and nitric acid solution is 3:1.Then, after with deionized water to acid processing Braiding carbon cloth rinsed, and the dry 10min at 80 DEG C.Braiding carbon cloth after rinsing is impregnated in vinyl trimethoxy In the alcoholic solution of siloxanes (10%, v/v), silanization treatment 1.0h is carried out.Then, it then immerses containing [2- (methacryloxypropyl Base) ethyl] trimethyl ammonium chloride (20wt%) and potassium peroxydisulfate (0.3wt%) mixed aqueous solution in, the free radical at 80 DEG C It polymerize 1.0h, obtains the braiding carbon cloth of the coating containing PMETAC, after being washed with deionized, the dry 10min at 80 DEG C.After washing The coating containing PMETAC braiding carbon cloth be soaked in concentration be 5 × 10^-3In the aqueous solution of the ammonium chloropalladate of mol/L, in dark Under the conditions of load 20min.

There is the braiding carbon cloth of the coating containing PMETAC of chlorine palladium acid group to immerse in copper plating bath load and carries out chemical deposition 10min obtains the braiding carbon cloth (CFCu) containing copper coating.The copper plating bath includes A liquid and B liquid, the A liquid be include NaOH (12g/L)、CuSO₄·5H₂O (13g/L) and KNaC₄H₄O₆·4H₂The aqueous solution of O (29g/L)；The B liquid is the water-soluble of HCHO Liquid (9.5mL/L)；The volume ratio of the A liquid and B liquid is 1:1.

At 25 DEG C, the braiding carbon cloth containing copper coating is exposed to 6h in air, is looked unfamiliar in the appearance of the copper coating At one layer of cuprous oxide, the braiding carbon cloth containing metal coating after oxidation is transferred in argon filling glove box, O₂And H₂O's Content is 0.8ppm, and at 350 DEG C, the edge of the braiding carbon cloth containing metal coating after oxidation is exposed to the lithium gold of liquid In category, lithium metal battery negative electrode material (CFCu-Li) is obtained.

Fig. 1, which is negative, is loaded with the braiding carbon cloth chemical deposition metallic copper of the coating containing PMETAC of chlorine palladium acid group, then carries out lithium Hot melt absorption procedure chart.From a of Fig. 1 as can be seen that by chemical deposition process, one layer deposited on braiding carbon cloth Uniform layers of copper, in air, the copper on the surface copper coating fabric (CFCu) are oxidized to cuprous oxide (Cu₂O), with a thickness of 2.0nm.After the lithium metal for contacting a certain amount of liquid, the lithium metal of liquid is driven into rapidly copper metal fabric and spontaneous expansion It dissipates, referred to as " lithium wicking ", and then obtains lithium metal battery negative electrode material (CFCu-Li).B in Fig. 1 is the wicking of different time lithium The digital picture of process.After it can be seen that 0.4s in the b of Fig. 1, liquid lithium metal will weave a greater part of of carbon cloth and soak Wet, after 0.6s, liquid lithium metal soaks braiding carbon cloth completely, and the speed of dipping is very fast.

The present embodiment by measurement room temperature under contact angle of the lithium drop on copper coating fabric (CFCu) obtained above come The surface wettability of CFCu is evaluated, as shown in Figure 2.Meanwhile Fig. 2 gives lithium drop connecing in other several matrix surfaces Feeler.Fig. 2 is contact angle of the lithium drop on different matrix surface.Figure it is seen that given matrix includes the present embodiment CFCu and carbon fiber CF, copper foil Cu foil and the copper-plated graphite foil Cu/graphite foil being prepared.It can be with from Fig. 2 To find out, contact angle of the lithium drop on carbon fiber CF is greater than 90 °, and contact angle of the lithium drop on copper foil Cu foil is about 80 °, Contact angle of the lithium drop on copper-plated graphite foil Cu/graphite foil is about 20 °, and contact angle of the lithium drop on CFCu is 0°.Obviously, the surface wettability for the CFCu that the present invention is prepared is more excellent.

It is analyzed using CFCu and above-mentioned CF of the X-ray diffractometer to embodiment 1, as a result as shown in Figure 3.Fig. 3 is The XRD diagram of CFCu and CF.Two samples all show typical carbon peak position (002).Unlike CF sample, CFCu sample is also Sharp metallic copper peak position (111), (200) and (220) is illustrated, illustrates that the coating of CFCu fiber surface is mainly highly crystalline Metallic copper.

The LMM power spectrum of CuXPS in obtained CFCu is analyzed, as a result as shown in Figure 4.Fig. 4 is the CFCu of embodiment 1 The LMM energy spectrum diagram of middle CuXPS.CFCu sample mainly shows Cu₂Two peak values of O and Ni metal, illustrate CFCu through peroxidating Processing surface covers a small amount of cuprous oxide.

The present embodiment also has detected diffusion speed of the lithium drop on copper coating fabric (CFCu) obtained above at 350 DEG C Degree, as a result as shown in Figure 5.Fig. 5 is that diffusion velocity of the lithium drop on the CFCu of embodiment 1 compares bar chart.Meanwhile Fig. 5 is also Give diffusion velocity of the lithium drop on copper facing carbon paper and copper foam under room temperature.From fig. 5, it can be seen that line density is high, arrangement The orderly and continuous metal-coated fabric of hole accelerates the diffusion velocity of lithium drop significantly.Existed by comparing lithium metal drop The metal-coated fabric of different line densities is (for example, CFCu-210 indicates that line density is that per inch 210 carbon lines contain copper coating Braiding carbon cloth) on diffusion velocity, it may be seen that the fabric of high linear density illustrates the most fast lithium drop rate of adsorption. Although copper coating carbon paper has high line density, the discontinuous characteristic of hole greatly hinders the diffusion of lithium drop.With institute Some sample comparisons, the metallic copper foam that hole is arranged unordered illustrate most slow drop diffusion velocity.

Obtained CFCu and CFCu-Li are scanned electron-microscope scanning analysis by the present embodiment, as a result as shown in fig. 6, Fig. 6 is The SEM of CYCu and CYCu-Li prepared by the SEM figure and embodiment 5 of CFCu and CFCu-Li prepared by the embodiment of the present invention 1 Figure.In Fig. 6, the top view that figure a is CFCu, the top view that figure b is CFCu-Li, figure c is the low of the CFCu-Li near lithium drop Multiplying power cross-sectional scans sem image, the high magnification cross-sectional scans sem image that figure d is the CFCu-Li near lithium drop, schemes e For the cross-sectional scans sem image of the CYCu (carbon line containing copper coating) near lithium drop, scheming f is the CYCu near lithium drop The top view of (carbon line containing copper coating), figure g are the cross-sectional scans far from the CYCu (carbon line containing copper coating) at lithium drop Sem image, figure h are the top view far from the CYCu (carbon line containing copper coating) at lithium drop.From fig. 6, it can be seen that in copper facing Carbon fabric and carbon line in, lithium drop has equably been adsorbed on above Cu coated fibre between fiber gap.At separate lithium drop CFCu compared with CYCu, fabric near lithium drop adsorbs relatively large number of liquid lithium.

The capacitance that the present embodiment obtains hot melt absorption lithium drop is 15mAh cm^-2A pair of of CFCu-Li be assembled into pair Claim half-cell, and detects the half-cell in constant current 1.0mA cm^-2Under plating/strip cycles capacity, as shown in Figure 7.Fig. 7 The symmetrical half-cell being assembled into for CFCu-Li is in 1.0mA cm^-2Under plating/strip cycles Capacity Plan.Meanwhile it being returned in Fig. 7 Half-cell that CFNi-Li and CFAg-Li are assembled into is gone out in constant current 1.0mA cm^-2Under plating/strip cycles capacity.From figure 7 as can be seen that the symmetrical half-cell that is assembled into of CFCu-Li presented under 100 plating/strip cycles it is very small and very stable Overpotential (10~20mV).In contrast, although the symmetrical half-cell of CFNi-Li composition also presents stable overpotential, But the relatively large resistance of Ni coating results in electrode polarization overpotential (20~110mV).In the half-cell that CFAg-Li is assembled into In, since Ag coating can react to form AgLi alloy with lithium ion repeatedly under plating/strip cycles, CFAg-Li assembling At half-cell overpotential it is relatively unstable (20~70mV).

Meanwhile the present embodiment is still using hot melt absorption lithium drop 15mAh cm^-2A pair of of CFCu-Li be assembled into symmetrical half Battery, then in constant current 2.0mA cm^-2Under carried out that/strip cycles cubic content measurement is electroplated, as shown in Figure 8.Fig. 8 is CFCu- The symmetrical half-cell that Li is assembled into is in constant current 2.0mA cm^-2Under circulation volume figure.Meanwhile load lithium is given in Fig. 8 Foam copper and the half-cell that is assembled into of lithium foil in constant current 2.0mA cm^-2Under obtained circulation volume curve.It can from Fig. 8 Out, CFCu-Li is assembled into symmetrical half-cell in high current and high circulation capacity (4.0mAh cm^-2) under still illustrate well Long circulating stability.However the half-cell that is assembled into of foam copper of hot melt absorption lithium illustrate be gradually increased overpotential (20~ 170mV).The half-cell (50~120mV) formed with thick and heavy lithium foil compares, and CFCu-Li is assembled into symmetrical half-cell still Present very small overpotential and long circulating stability (20~50mV).

The present embodiment carries out obtained CFCu-Li/strip cycles are electroplated, and to the 50th plating/strip cycles after CFCu-Li is scanned electron microscope analysis, as a result as shown in figure 9, the SEM figure that Fig. 9 is CFCu-Li prepared by embodiment 1.In Fig. 9, Scheme the low range scanning electron microscope image that a is the CFCu-Li after the 50th plating/strip cycles, figure b is the 50th plating/removing The high magnification scanning electron microscope image of CFCu-Li after circulation.Meanwhile it is given in Fig. 9 to after the 50th plating/strip cycles Lithium foil be scanned electron microscope analysis, wherein figure c is the low range scanning electron microscope of the lithium foil after the 50th plating/strip cycles Image, figure d are the high magnification scanning electron microscope image of the lithium foil after the 50th plating/strip cycles.From fig. 9, it can be seen that CFCu- Li electrode surface after 50 plating/strip cycles is still very smooth, is covered by micron-sized lithium metal particle.However lithium is golden Belong to foil after same number plating/strip cycles electrode surface but by apparent destruction.The lithium metal that these are destroyed is very It is easily separated from electrode and loses and circuit connection and then become useless " dead lithium ", will lead to quick lithium metal consumption and excessively poor Plating/strip cycles.

Above-mentioned CFCu and CFCu-Li are analyzed using X-ray diffractometer, as shown in Figure 10.Figure 10 is in embodiment 1 CFCu and CFCu-Li XRD diagram.Wherein, the XRD diagram that the figure a in Figure 10 is CFCu and CFCu-Li.Meanwhile it being returned in Figure 10 Gone out CFNi and CFNi-Li XRD diagram (see figure b) and CFAg and CFAg-Li in Figure 10 XRD diagram (see the figure in Figure 10 c).From fig. 10 it can be seen that the XRD spectrum of CFCu-Li and CFCu all shows typical carbon (001) characteristic peak.But CFCu-Li Carbon peak position significantly moved left to 24.0 ° from 25.5 °, illustrate that a part of lithium has been embedded in the form of lithium ion in reflow process Inside carbon fabric.CFCu-Li additionally shows the characteristic peak (36.2 °) and (65.0 °) of lithium metal simultaneously, illustrates lithium metal Via absorption into coppered carbon fabric the inside.The XRD spectrum of CFNi-Li is similar with CFCu-Li.However the XRD spectrum of CFAg-Li But present the sharp AgLi alloy peak position of new three, this with the metal composite in CFCu-Li or CFNi-Li obviously not Together.

CFCu-Li obtained above is subjected to continuous bend under differently curved radius, while monitoring the face electricity of CFCu-Li Resistive, as shown in figure 11.Figure 11 is the surface resistance variation diagram of CFCu-Li continuous bend under differently curved radius.Fatigue is surveyed Specific step is as follows for examination: carrying out continuous bend under conditions of bending radius is 5.0mm first, then reduces bending radius extremely 2.0mm continues mechanics bending.Meanwhile CFNi-Li is given in Figure 11, CFAg-Li and condition of equivalent thickness lithium metal foil it is tired Labor test.It can be seen from figure 11 that CFCu-Li can be with continuous bend 2000 times and face under conditions of bending radius is 5.0mm Resistance is not substantially change.Even if further decreasing bending radius to be bent to 2.0mm, still can be bent 900 times. However the lithium metal foil of condition of equivalent thickness (under conditions of bending radius 5.0mm) has only been bent 840 just fractures, illustrates its Poor fatigue resistance.CFNi-Li sample presents relatively good flexibility, can bear under conditions of bending radius 5.0mm Then 1400 bendings are broken.The mechanical stability that CFAg-Li can be remained intact under conditions of bending radius 5.0mm, when It is broken after 100 bendings when bending radius is reduced to 2.0mm.In testing fatigue, the metal of adsorbing metal lithium is applied Layer carbon cloth all shows preferable anti-fatigue performance.Wherein CFCu-Li illustrates best mechanical stability.To illustrate this reality It applies the lithium metal battery negative electrode material that example is prepared and shows excellent mechanical stability in bending process repeatedly.

The metal coating carbon cloth of absorption lithium can directly be cut as negative electrode tab, then with LiFePO4 (LFP) for positive plate, Centre separates positive and negative anodes using commercial polypropylene isolation film.According to electrode size (40L cm^-2) injection electrolyte.Here it uses It is to be added in DOL/DME (DME:DOL=1:1 (V/V)) containing 2wt%LiNO₃1mol/L LiTFSI electrolyte be electrolysed Liquid.Stainless steel coin battery is finally assembled into argon filling glove box.

The present embodiment is in 0.5~8.0mA cm^-2Different current densities under carry out charge-discharge test, using new prestige battery survey The chemical property of instrument test battery is tried, charging/discharging voltage is limited in 2.8~4.0V, and test condition is room temperature, obtains its multiplying power Performance curve is as shown in figure 12.Figure 12 is the high rate performance curve of lithium metal battery prepared by embodiment 1.Reality is given in Figure 12 The lithium metal battery of the preparation of example 1 is applied in 0.5~8.0mA cm^-2Different current densities under high rate performance curve；Meanwhile Figure 12 In give the battery for using lithium foil (Li foil) to obtain for cathode in 0.5~8.0mA cm^-2Different current densities under High rate performance curve.In figure 12 it can be seen that the present embodiment uses CFCu-Li to exist respectively for the lithium metal battery of cathode 0.5mA cm^-2、1.0mAcm^-2、2.0mA cm^-2With 4.0mA cm^-2With 8.0mA cm^-2Multiplying power under carry out 10 cycle charge discharges Electricity, the specific discharge capacity under each current density be respectively 161mAh/g, 138mAh/g, 119mAh/g, 95mAh/g and 74mAh/g.When current density returns to 1.0mA cm^-2When, specific discharge capacity 133mAh/g.Thus, there is preferable times Rate performance.And the battery for using lithium foil (Li foil) to obtain for cathode is respectively in 0.5mA cm^-2、1.0mA cm^-2、2.0mA cm^-2With 4.0mA cm^-2With 8.0mA cm^-2Multiplying power under carry out 10 cycle charge-discharges, the electric discharge ratio under each current density Capacity is respectively 146mAh/g, 95mAh/g, 57mAh/g, 1.2mAh/g and 0.95mAh/g.When current density returns to 1.0mA cm^-2When, specific discharge capacity 92mAh/g, high rate performance is poor.

The present embodiment is in 8.0mA cm^-2Under conditions of carry out charge-discharge test, using new prestige cell tester test battery Chemical property, charging/discharging voltage is limited in 2.8~4.0V, and test condition is room temperature, obtains its first charge-discharge curve such as Shown in Figure 13.Figure 13 is the first charge-discharge curve for the lithium metal battery that CFCu-Li prepared by embodiment 1 is cathode.Meanwhile scheming The first charge-discharge curve that the battery that cathode obtains is made using lithium foil (Li foil) is given in 13.It can from Figure 13 Out, CFCu-Li is that the lithium metal battery of cathode still can show higher output voltage (3.3V) He Gao electricity under high currents Capacity (74mAh/g).But Li foil be cathode the voltage that is exported under same electric current of lithium metal battery and capacitance it is several It is zero.Lithium metal battery negative electrode material to illustrate that the present embodiment is prepared shows excellent fast charging and discharging Energy.

The present embodiment is in 1.0mA cm^-2Under conditions of carry out charge-discharge test, using new prestige cell tester test battery Chemical property, charging/discharging voltage is limited in 2.8~4.0V, and test condition is room temperature, obtains its cycle performance curve and library Human relations efficiency curve is as shown in figure 14.Figure 14 is the cycle performance curve and coulombic efficiency song of lithium metal battery prepared by embodiment 1 Line.It is seen from figure 14 that lithium metal battery provided by the invention is in 1.0mA cm^-2Under conditions of, cycle charge-discharge 500 times Afterwards, capacity retention ratio 95%, coulombic efficiency are more stable close to 100%.Thus, there is preferable cycle performance.

Embodiment 2

Braiding carbon cloth is immersed in acid solution, at 60 DEG C, is ultrasonically treated 60min.The acid solution includes sulfuric acid solution And nitric acid solution, the volume ratio of the sulfuric acid solution and nitric acid solution are 3:1.Then, with deionized water to acid treated compile It knits carbon cloth to be rinsed, and the dry 10min at 80 DEG C.Braiding carbon cloth after rinsing is impregnated in vinyl trimethoxy silicon oxygen In the alcoholic solution of alkane (10%, v/v), silanization treatment 1.0h is carried out.Then, it then immerses containing [2- (methacryloxy) Ethyl] trimethyl ammonium chloride (20wt%) and potassium peroxydisulfate (0.3wt%) mixed aqueous solution in, the free radical polymerization at 80 DEG C 1.0h obtains the braiding carbon cloth of the coating containing PMETAC, after being washed with deionized, the dry 10min at 80 DEG C.Containing after washing It is 5 × 10 that the braiding carbon cloth of PMETAC coating, which is soaked in concentration,^-3In the aqueous solution of the ammonium chloropalladate of mol/L, in dark condition Lower load 20min.

There is the braiding carbon cloth of the coating containing PMETAC of chlorine palladium acid group to immerse in nickel-plating liquid load and carries out chemical deposition 10min obtains the braiding carbon cloth (CFNi) containing nickel coating.The nickel-plating liquid includes a liquid and b liquid, and a liquid is to include Ni₂SO₄·5H₂The aqueous solution of O (40g/L), sodium citrate (20g/L) and lactic acid (10g/L)；The b liquid is dimethylamine borane The aqueous solution of (7.5g/L)；The volume ratio of a liquid and b liquid is 10:1.

At 25 DEG C, the braiding carbon cloth containing nickel coating is exposed to 6h in air, is looked unfamiliar in the appearance of the nickel coating The NiO thin layer for being 2.0nm at a layer thickness, is transferred to argon filling glove box for the braiding carbon cloth containing metal coating after oxidation In, O₂And H₂The content of O is 0.8ppm, at 350 DEG C, by the edge exposure of the braiding carbon cloth containing metal coating after oxidation In the lithium metal of liquid, lithium metal battery negative electrode material (CFNi-Li) is obtained.

Pass through the digital picture of the lithium metal of observation of liquid state lithium wicking process on CFNi, it is known that, after 60s, liquid lithium gold Category soaks the more than half part for weaving carbon cloth, and after 150s, liquid lithium metal soaks braiding carbon cloth completely, the speed of dipping It spends relatively slow.

The present embodiment contact angle of lithium drop on nickel coating fabric (CFNi) obtained above at 350 DEG C by measurement The surface wettability of CFNi is evaluated, the experimental results showed that, contact angle of the lithium drop on CFNi is 0 °.Obviously, of the invention The surface wettability for the CFNi being prepared is more excellent.

The present embodiment also has detected diffusion speed of the lithium drop on nickel coating fabric (CFNi) obtained above at 350 DEG C Degree is 0.012m min^-1。

The capacitance that the present embodiment obtains hot melt absorption lithium drop is 15mAh cm^-2A pair of of CFNi-Li be assembled into pair Claim half-cell, and detects the half-cell in constant current 1.0mA cm^-2Under plating/strip cycles capacity, as shown in Figure 7.From The symmetrical half-cell that Fig. 7 can be seen that CFNi-Li composition also presents stable overpotential, but the relatively large electricity of Ni coating Resistance results in relatively large electrode polarization overpotential (20~110mV).

Above-mentioned CFNi and CFNi-Li are analyzed using X-ray diffractometer, as shown in the figure b in Figure 10.It can from Figure 10 To find out, the XRD spectrum of CFNi-Li and CFNi all show typical carbon (001) characteristic peak.But the carbon peak position of CFNi-Li from 25.5 ° have significantly moved left to 24.0 °, illustrate that a part of lithium has been embedded in carbon fabric in the form of lithium ion in reflow process Face.Simultaneously CFNi-Li additionally show the characteristic peak (36.2 °) and (65.0 °) of lithium metal, illustrate lithium metal adsorbed into Enter inside nickel plating carbon fabric.

CFNi-Li obtained above is subjected to continuous bend in the case where bending radius is 5.0mm, while monitoring CFNi-Li's Surface resistance variation, as shown in figure 11.It can be seen from figure 11 that CFNi-Li sample shows compared with the lithium metal foil of condition of equivalent thickness Preferable flexibility can bear under conditions of bending radius 5.0mm 1400 bendings.To illustrate prepared by the present embodiment Obtained lithium metal battery negative electrode material shows excellent mechanical stability in bending process repeatedly.

The present embodiment directly cuts CFNi-Li as negative electrode tab, intermediate then with LiFePO4 (LFP) for positive plate Positive and negative anodes are separated using commercial polypropylene isolation film.According to electrode size (40L cm^-2) injection electrolyte.Here using It is added in DOL/DME (DME:DOL=1:1 (V/V)) and contains 2wt%LiNO₃The obtained electrolysis of 1mol/L LiTFSI electrolyte Liquid.Stainless steel coin battery is finally assembled into argon filling glove box.

The present embodiment is in 1.0mA cm^-2Under conditions of carry out charge-discharge test, using new prestige cell tester test described in The chemical property of battery, charging/discharging voltage are limited in 2.8~4.0V, and test condition is room temperature, and battery cycle charge-discharge 500 times Afterwards, coulombic efficiency is more stable close to 100%.

Embodiment 3

There is the braiding carbon cloth of the coating containing PMETAC of chlorine palladium acid group to immerse in silver plating liquid load and carries out chemical deposition 10min obtains the braiding carbon cloth (CFAg) containing silvering.The silver plating liquid be include [Ag (NH₃)₂]NO₃(1g/L) and winestone The aqueous solution of sour potassium sodium (5g/L).

At 25 DEG C, the braiding carbon cloth containing silvering is exposed to 6h in air, is looked unfamiliar in the appearance of the silvering The Ag for being 2.0nm at a layer thickness₂The braiding carbon cloth containing metal coating after oxidation is transferred in argon filling glove box by O, O₂And H₂The content of O is that the edge of the braiding carbon cloth containing metal coating after oxidation is exposed to liquid at 350 DEG C by 0.8ppm In the lithium metal of state, lithium metal battery negative electrode material (CFAg-Li) is obtained.

Pass through the digital picture of the lithium metal of observation of liquid state lithium wicking process on CFAg, it is known that, after 5.0s, liquid lithium gold Category soaks the more than half part for weaving carbon cloth, and after 10s, liquid lithium metal soaks braiding carbon cloth completely, the speed of dipping It spends very fast.

The present embodiment contact angle of lithium drop on silver coating fabric (CFAg) obtained above at 350 DEG C by measurement The surface wettability of CFAg is evaluated, the experimental results showed that, contact angle of the lithium drop on CFAg is 0 °.Obviously, of the invention The surface wettability for the CFAg being prepared is more excellent.

The present embodiment also has detected diffusion speed of the lithium drop on silver coating fabric (CFAg) obtained above at 350 DEG C Degree is 0.21mmin^-1。

The capacitance that the present embodiment obtains hot melt absorption lithium drop is 15mAh cm^-2A pair of of CFAg-Li electrode assembling At symmetrical half-cell, and the half-cell is detected in constant current 1.0mA cm^-2Under plating/strip cycles capacity, such as Fig. 7 institute Show.Although from figure 7 it can be seen that relatively unstable by the overpotential that the symmetrical half-cell that CFAg-Li is assembled into is shown in the circulating cycle Qualitative (20~70mV), but still can operation fully.

Above-mentioned CFAg and CFAg-Li are analyzed using X-ray diffractometer, as shown in the figure c in Figure 10.It can from Figure 10 To find out, the XRD spectrum of CFAg-Li presents the sharp AgLi alloy peak position of new three, this and CFCu-Li or CFNi- Metal composite in Li is significantly different.

CFAg-Li obtained above is subjected to continuous bend under differently curved radius, while monitoring the face electricity of CFAg-Li Resistive, as shown in figure 11.Specific step is as follows for testing fatigue: carrying out under conditions of bending radius is 5.0mm first continuous Then bending reduces bending radius to 2.0mm continuation mechanics bending.It can be seen from figure 11 that CFAg-Li is in bending radius 2000 repetition mechanical bends can be born under conditions of 5.0mm and keep surface resistance almost unchanged.When bending radius is further When being reduced to 2.0mm, 100 bendings can be still born.To illustrate the lithium metal battery that the present embodiment is prepared Negative electrode material shows excellent mechanical stability in bending process repeatedly.

The present embodiment directly cuts CFAg-Li as negative electrode tab, intermediate then with LiFePO4 (LFP) for positive plate Positive and negative anodes are separated using commercial polypropylene isolation film.According to electrode size (40Lcm^-2) injection liquid electrolyte.Here it uses It is to be added in DOL/DME (DME:DOL=1:1 (V/V)) containing 2wt%LiNO₃The obtained electricity of 1mol/L LiTFSI electrolyte Liquid is solved, stainless steel coin battery is finally assembled into argon filling glove box.

Embodiment 4

The specification of carbon paper:

Carbon paper is with a thickness of 100~200 μm, surface density: 4.0~8.0mg cm^-2。

Carbon paper is immersed in acid solution, at 25 DEG C, is ultrasonically treated 60min.The acid solution includes sulfuric acid solution and nitre The volume ratio of acid solution, the sulfuric acid solution and nitric acid solution is 3:1.Then, with deionized water to acid treated carbon paper into Row rinsing, and the dry 10min at 80 DEG C.Carbon paper after rinsing is impregnated in vinyl trimethoxy siloxanes (15%, v/v) Alcoholic solution in, carry out silanization treatment 0.5h.Then, it then immerses containing [2- (methacryloxy) ethyl] trimethyl chlorine In the mixed aqueous solution for changing ammonium (20wt%) and potassium peroxydisulfate (0.3wt%), free radical polymerization 1.0h, is contained at 80 DEG C The carbon paper of PMETAC coating, after being washed with deionized, the dry 10min at 80 DEG C.The carbon of the coating containing PMETAC after washing It is 3 × 10 that paper, which is soaked in concentration,^-3In the aqueous solution of the ammonium chloropalladate of mol/L, 20min is loaded in dark conditions.

There is the carbon paper of the coating containing PMETAC of chlorine palladium acid group to immerse load and carry out electrochemical deposition 10min in copper plating bath, Obtain the carbon paper (CPCu) containing copper coating.The copper plating bath includes A liquid and B liquid, the A liquid be include NaOH (12g/L), CuSO₄·5H₂O (13g/L) and KNaC₄H₄O₆·4H₂The aqueous solution of O (29g/L)；The B liquid is the aqueous solution (9.5mL/ of HCHO L)；The volume ratio of the A liquid and B liquid is 1:1.

At 50 DEG C, the carbon paper containing copper coating is exposed to 6h in air, is generated in the outer surface of the copper coating A layer thickness is the cuprous oxide of 2.0nm, the carbon paper containing metal coating after oxidation is transferred in argon filling glove box, O₂With H₂The content of O is that the edge of the carbon paper containing metal coating after oxidation is exposed to the lithium of liquid at 350 DEG C by 0.8ppm In metal, lithium metal battery negative electrode material (CPCu-Li) is obtained.

Pass through the digital picture of the lithium metal of observation of liquid state lithium wicking process on CPCu, it is known that, after 20s, liquid lithium gold Category soaks the more than half part of carbon paper.After 38s, liquid lithium metal soaks carbon paper completely, and the speed of dipping is relatively fast.

The present embodiment evaluates CPCu's by measuring contact angle of the lithium drop on CPCu obtained above at 350 DEG C Surface wettability, the experimental results showed that, contact angle of the lithium drop on CPCu is 0 °.Obviously, the present invention is prepared The surface wettability of CPCu is more excellent.

It is 0.06m that the present embodiment, which also has detected diffusion velocity of the lithium drop on CPCu obtained above at 350 DEG C, min^-1, as a result as shown in Figure 5.From fig. 5, it can be seen that although diffusion rate of the lithium drop on CPCu obtained above compares CFCu Diffusion rate more slowly, but is still better than commercialized foam copper.

CPCu-Li obtained above is subjected to continuous bend under differently curved radius, while monitoring the face electricity of CPCu-Li Resistive.Specific step is as follows for testing fatigue: carrying out continuous bend under conditions of bending radius is 5.0mm first, then subtracts Small-bend radius continues mechanics to 2.0mm and is bent.The experimental results showed that CPCu-Li can be under conditions of bending radius 2.0mm It bears 50 repetition mechanical bends and keeps surface resistance almost unchanged；1000 can be born under conditions of bending radius 5.0mm It is secondary to repeat mechanical bend and keep surface resistance almost unchanged.To illustrate the lithium metal battery cathode material that the present embodiment is prepared Material shows excellent mechanical stability in bending process repeatedly.

The present embodiment directly cuts CPCu-Li as negative electrode tab, intermediate then with LiFePO4 (LFP) for positive plate Positive and negative anodes are separated using commercial polypropylene isolation film.According to electrode size (40L cm^-2) injection liquid electrolyte.Here it uses It is to be added in DOL/DME (DME:DOL=1:1 (V/V)) and contain 2wt%LiNO₃1mol/L LiTFSI electrolyte obtain Electrolyte is finally assembled into stainless steel coin battery in argon filling glove box.

Embodiment 5

The specification of carbon line:

The cross-sectional diameter of carbon line is 200 μm, and line density is 0.24mg cm^-1, carbon line length is 5.0cm.

Carbon line is immersed in acid solution, at 25 DEG C, is ultrasonically treated 60min.The acid solution includes sulfuric acid solution and nitre The volume ratio of acid solution, the sulfuric acid solution and nitric acid solution is 3:1.Then, with deionized water to acid treated carbon line into Row rinsing, and the dry 10min at 80 DEG C.Carbon paper after rinsing is impregnated in vinyl trimethoxy siloxanes (15%, v/v) Alcoholic solution in, carry out silanization treatment 0.5h.Then, it then immerses containing [2- (methacryloxy) ethyl] trimethyl chlorine In the mixed aqueous solution for changing ammonium (20wt%) and potassium peroxydisulfate (0.3wt%), free radical polymerization 1.0h, is contained at 80 DEG C The carbon line of PMETAC coating, after being washed with deionized, the dry 10min at 80 DEG C.The carbon of the coating containing PMETAC after washing It is 3 × 10 that line, which is soaked in concentration,^-3In the aqueous solution of the ammonium chloropalladate of mol/L, 20min is loaded in dark conditions.

There is the carbon line of the coating containing PMETAC of chlorine palladium acid group to immerse load and carry out electrochemical deposition 10min in copper plating bath, Obtain the carbon line (CYCu) containing copper coating.The copper plating bath includes A liquid and B liquid, the A liquid be include NaOH (12g/L), CuSO₄·5H₂O (13g/L) and KNaC₄H₄O₆·4H₂The aqueous solution of O (29g/L)；The B liquid is the aqueous solution (9.5mL/ of HCHO L)；The volume ratio of the A liquid and B liquid is 1:1.

At 50 DEG C, the carbon line containing copper coating is exposed to 6h in air, is generated in the outer surface of the copper coating A layer thickness is the cuprous oxide of 2.0nm, the carbon line containing metal coating after oxidation is transferred in argon filling glove box, O₂With H₂The content of O is that the edge of the carbon line containing metal coating after oxidation is exposed to the lithium of liquid at 350 DEG C by 0.8ppm In metal, lithium metal battery negative electrode material (CYCu-Li) is obtained.

Figure 15 is the digital picture of lithium metal lithium wicking process on the CYCu of embodiment 5 of liquid.Pass through observation of liquid state Lithium metal lithium wicking process on CYCu digital picture, it is known that, after 1.0s, liquid lithium metal soaks the half of carbon line It is wet.After 2.0s, liquid lithium metal soaks carbon line completely, and the speed of dipping is relatively fast.

The present embodiment evaluates CYCu's by measuring contact angle of the lithium drop on CYCu obtained above at 350 DEG C Surface wettability, the experimental results showed that, contact angle of the lithium drop on CYCu is 0 °.Obviously, the present invention is prepared The surface wettability of CYCu is more excellent.

It is 1.5m that the present embodiment, which also has detected diffusion velocity of the lithium drop on CYCu obtained above at 350 DEG C, min^-1。

Obtained CYCu and CYCu-Li are scanned electron-microscope scanning analysis by the present embodiment, as a result as shown in Figure 6.Wherein, Scheme the cross-sectional scans sem image that e is the CYCu (carbon line containing copper coating) near lithium drop, figure f is near lithium drop The top view of CYCu (carbon line containing copper coating), figure g are the cross section far from the CYCu (carbon line containing copper coating) at lithium drop Scanning electron microscope image, figure h are the top view far from the CYCu (carbon line containing copper coating) at lithium drop.From fig. 6, it can be seen that In copper-plated carbon fabric and carbon line, lithium drop has equably been adsorbed on above Cu coated fibre between fiber gap.With separate lithium liquid CFCu at drop is compared with CYCu, and the fabric near lithium drop adsorbs relatively large number of liquid lithium.

The capacitance that the present embodiment obtains hot melt absorption lithium drop is 1.1mAh cm^-2A pair of of CYCu-Li be assembled into pair Claim half-cell, and detects the half-cell in constant current 0.1mA cm^-2Under plating/strip cycles capacity, as shown in figure 16.Figure The 16 symmetrical half-cells being assembled into for CYCu-Li in embodiment 5 are in 0.1mA cm^-2Under plating/strip cycles Capacity Plan.Together When, Cu wire-Li (electrode that the common yarn absorption Li containing copper coating is obtained) is assembled into symmetrical half is given in Figure 16 Battery is in 0.1mA cm^-2Under plating/strip cycles Capacity Plan.As can be seen from Figure 16, symmetrical half electricity that CYCu-Li is assembled into Chi Gao electric current per unit length 0.1mA cm^-1Under present smaller and very stable overpotential (120mV).And be electroplated at 200/ Keep overpotential constant substantially in strip cycles.In contrast, the symmetrical half-cell that Cu wire-Li is assembled into is not shown only Biggish overpotential (220mV), and in 50 plating/strip cycles, overpotential increases suddenly.To illustrate the present embodiment The lithium metal threadiness negative electrode material being prepared has more excellent coulombic efficiency and cyclical stability.

CYCu-Li obtained above is subjected to continuous bend under differently curved radius, while monitoring the face electricity of CYCu-Li Resistive.Specific step is as follows for testing fatigue: carrying out continuous bend under conditions of bending radius is 5.0mm first, then subtracts Small-bend radius continues mechanics to 2.0mm and is bent.The experimental results showed that CYCu-Li can be under conditions of bending radius 2.0mm It bears 1000 repetition mechanical bends and keeps surface resistance almost unchanged；It can be born under conditions of bending radius 5.0mm 2000 repetition mechanical bends and keep surface resistance it is almost unchanged.To illustrate that the lithium metal battery that the present embodiment is prepared is negative Pole material shows excellent mechanical stability in bending process repeatedly.

The present embodiment directly cuts CYCu-Li as negative electrode tab, intermediate then with LiFePO4 (LFP) for positive plate Positive and negative anodes are separated using commercial polypropylene isolation film.According to electrode size (40L cm^-2) injection electrolyte.Here using It is added in DOL/DME (DME:DOL=1:1 (V/V)) and contains 2wt%LiNO₃1mol/L LiTFSI electrolyte obtain electrolyte. Stainless steel coin battery is finally assembled into argon filling glove box.

The present embodiment is in 30 μ A cm^-1Under conditions of carry out charge-discharge test, the electricity is tested using new prestige cell tester The chemical property in pond, charging/discharging voltage are limited in 2.8~4.0V, and test condition is room temperature, obtain its first charge-discharge curve As shown in figure 17.Figure 17 is the charging and discharging curve for the lithium metal battery that CYCu-Li prepared by embodiment 5 is cathode.Wherein, Figure 17 In give first charge-discharge curve, the curve after cycle charge-discharge 100 times, the curve after cycle charge-discharge 200 times and circulation Curve after charge and discharge 300 times.As can be seen from Figure 17, CYCu-Li is that the lithium metal battery of cathode is filled by 100 circulations Capacitance holding is basically unchanged after electric discharge, and capacitance still can keep 85% or more after 300 cycle charge-discharges.To Illustrate that the lithium metal threadiness negative electrode material that the present embodiment is prepared has excellent coulombic efficiency and cyclical stability.

The present embodiment is in 30 μ A cm^-1Under conditions of carry out charge-discharge test, the electricity is tested using new prestige cell tester The chemical property in pond, charging/discharging voltage are limited in 2.8~4.0V, and test condition is room temperature, obtain its cycle performance curve and Coulombic efficiency curve is as shown in figure 18.Figure 18 is the cycle performance curve and coulombic efficiency of lithium metal battery prepared by embodiment 5 Curve.As can be seen from Figure 18, lithium metal battery provided by the invention is in 30 μ A cm^-1Under conditions of, cycle charge-discharge 400 times Afterwards, capacity retention ratio 80%, coulombic efficiency are more stable close to 100%.Thus, there is preferable cycle performance.

The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one The widest scope of cause.

Claims

1. a kind of preparation method of the carbon material containing metal coating, comprising the following steps:

A) carbon material is carried out in acid solution to surface oxidation, then mixed with catalyst solution, obtains catalyst supported on surface Carbon material；

B) carbon material of the catalyst supported on surface is waited for depositing in plating solution in metal, obtains the carbon containing metal coating Material.

2. preparation method according to claim 1, which is characterized in that the carbon material includes carbon fiber, carbon line, braiding carbon Cloth, on-woven carbon cloth, carbon paper or carbon felt.

3. preparation method according to claim 1, which is characterized in that step A) in, carbon material is carried out in acid solution Surface oxidation specifically: carbon material is immersed in acid solution, at 25~60 DEG C, is ultrasonically treated 5~60min；Or by carbon material It immerses in acid solution, at 25~60 DEG C, 5~60min of oxygen plasma treatment；

The catalyst solution is the aqueous solution of ammonium chloropalladate, and the concentration of the aqueous solution of the ammonium chloropalladate is 1 × 10^-4~5 × 10^-3mol/L；

4. preparation method according to claim 1, which is characterized in that step A) in, after the surface oxidation further include:

Carbon material after the surface oxidation is subjected to silanization treatment, then is immersed containing [2- (methacryloxy) ethyl] In the mixed solution of trimethyl ammonium chloride and potassium peroxydisulfate, the carbon material of the coating containing PMETAC is obtained after Raolical polymerizable.

5. the preparation method according to claim 4, which is characterized in that the reagent that the silanization treatment uses is vinyl The alcoholic solution of trimethoxy siloxane；

In the alcoholic solution of the vinyl trimethoxy siloxanes, the volumn concentration of vinyl trimethoxy siloxanes is 5 ~20%；

The time of the silanization treatment is 0.5~1.0h；

In mixed solution containing [2- (methacryloxy) ethyl] trimethyl ammonium chloride and potassium peroxydisulfate, [2- (methyl-prop Alkene acyloxy) ethyl] trimethyl ammonium chloride concentration be 5~30wt%；The concentration of potassium peroxydisulfate is 0.1~0.5wt%；

The temperature of the Raolical polymerizable is 80~120 DEG C, and the time of the Raolical polymerizable is 0.5~2.0h.

6. preparation method according to claim 1, which is characterized in that step B) in, the metal packet in the metal coating Include copper, nickel, silver, zinc, aluminium or manganese.

7. the carbon material containing metal coating of claim 1~6 any one preparation method preparation.

8. a kind of preparation method of lithium metal battery negative electrode material, comprising the following steps:

The hot melt absorption that the carbon material containing metal coating is carried out to lithium at 350~400 DEG C, it is negative to obtain lithium metal battery Pole material；

The carbon material containing metal coating is the carbon material as claimed in claim 7 containing metal coating.

9. preparation method according to claim 8, which is characterized in that before the hot melt absorption further include:

10. the lithium metal battery negative electrode material of claim 8~9 any one preparation method preparation.

11. a kind of lithium metal battery, including anode, cathode, diaphragm and electrolyte, the cathode include described in any one of claim 10 Lithium metal battery negative electrode material.