CN110061190A - Liquid metal matrix self-healing lithium cell negative pole and preparation method and lithium ion battery - Google Patents

Liquid metal matrix self-healing lithium cell negative pole and preparation method and lithium ion battery Download PDF

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CN110061190A
CN110061190A CN201810544833.2A CN201810544833A CN110061190A CN 110061190 A CN110061190 A CN 110061190A CN 201810544833 A CN201810544833 A CN 201810544833A CN 110061190 A CN110061190 A CN 110061190A
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liquid metal
silicon
nano particle
lithium cell
healing
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邓永红
韩兵
张田
杜磊磊
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Southwest University of Science and Technology
Southern University of Science and Technology
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Southwest University of Science and Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1395Processes of manufacture of electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/626Metals
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to technical field of lithium ion, specifically provide a kind of liquid metal matrix self-healing lithium cell negative pole and preparation method and lithium ion battery.The liquid metal matrix self-healing lithium cell negative pole includes negative current collector and the negative electrode material for being attached to the negative current collector surface, and the negative electrode material includes the composite material of liquid metal nano particle and silicon, binder;According to mass ratio, the composite material of the liquid metal nano particle and silicon: binder=(9~90): 1;Wherein, in the composite material of the liquid metal nano particle and silicon, the mass ratio of liquid metal nano particle and silicon is 1:(1~5).When cathode of the invention is assembled into lithium ion battery, liquid metal nano particle can carry out self-regeneration to silicon materials, to have overlength cycle characteristics, and quick charge may be implemented, can carry out high-multiplying power discharge.

Description

Liquid metal matrix self-healing lithium cell negative pole and preparation method and lithium ion battery
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of liquid metal matrix self-healing lithium cell negative pole and system Preparation Method and lithium ion battery.
Background technique
With the demand for development to technologies such as energy storage device higher energy density, long circulating and ultrafast charge and discharge, exploitation is more Outstanding electrode material of new generation is particularly important.Its theoretical specific capacity of business lithium battery uses at present graphite cathode material Only 372mAh/g, it is difficult to meet the application demand of novel high-energy metric density lithium battery.Although lithium an- ode has very high Specific capacity (3860mAh/g), but Li dendrite easy to form during circulating battery, service life are not grown, while being easy to cause peace Full problem.In comparison, silicium cathode has higher theoretical specific capacity (4212mAh/g (Li4.4Si)), and discharge platform compared with It is low, it is not easy that Li dendrite is precipitated, security performance is more preferable.However, the practical application of silicium cathode still has huge challenge, major embodiment In the following aspects: 1) charge and discharge cycles during, the insertion of lithium ion and abjection can make material volume occur 300% with On variation, make material gradually dusting, eventually lead to electrode active material and collector and be detached from, destroy conductive network, lead to electricity Pond cycle performance reduces.2) silicon self-conductance rate is lower.3) bulk effect makes silicon be difficult to form stable consolidate in the electrolytic solution Body electrolyte interface (SEI) film, reduces coulombic efficiency while exacerbating the decaying of capacity.
Summary of the invention
Cause SEI film unstable for current silicon substrate lithium ion battery volume expansion in charge and discharge process is excessive, finally Lead to problems such as battery cycle life short, the present invention provides a kind of liquid metal matrix self-healing lithium cell negative pole and preparation method.
And liquid metal matrix self-healing lithium cell negative pole the answering in lithium ion battery obtained by above-mentioned preparation method With.
For achieving the above object, technical scheme is as follows:
A kind of liquid metal matrix self-healing lithium cell negative pole, including negative current collector and it is attached to the negative current collector surface Negative electrode material, the negative electrode material includes the composite material of liquid metal nano particle and silicon, binder;
According to mass ratio, the composite material of the liquid metal nano particle and silicon: binder=(9~90): 1;
Wherein, in the composite material of the liquid metal nano particle and silicon, the quality of liquid metal nano particle and silicon Than for 1:(1~5).
Correspondingly, a kind of preparation method of liquid metal matrix self-healing lithium cell negative pole, at least includes the following steps:
The suspension of liquid metal nano particle is ultrasonically treated by step S01. with Si powder, is obtained liquid metal and is received The composite material of rice grain and silicon;
Step S02. disperses the composite material of binder and the liquid metal nano particle and silicon in solvent, is made The slurry of acquisition is then coated on negative current collector surface, through drying, cuts processing, obtain liquid metal matrix by slurry Self-healing lithium cell negative pole.
And a kind of lithium ion battery, including anode, cathode, diaphragm, electrolyte and battery case, the cathode are as above The liquid metal matrix self-healing lithium cell negative pole or the cathode are using liquid metal matrix self-healing lithium electricity as described above The preparation method of cathode is prepared.
The beneficial effect of liquid metal matrix self-healing lithium cell negative pole of the present invention is:
Compared with the existing technology, liquid metal matrix self-healing lithium cell negative pole of the invention does not need to add additional conduction Agent, but directly improve the content of silicon materials using liquid metal nano particle as self-repair material and conductive agent, used When on lithium ion battery, there is good interfacial contact and ultralow resistivity, liquid metal nano particle can be to silicon Material carries out self-regeneration, to have overlength cycle characteristics, and quick charge may be implemented, can carry out high-multiplying power discharge.
The preparation method of liquid metal matrix self-healing lithium cell negative pole provided by the invention, preparation process is few, high production efficiency, Production cost is low, and seamless connection, easily realization industrialization can be realized with present industry line.
Lithium ion battery provided by the invention can be effective since cathode uses liquid metals base self-healing lithium cell negative pole Ground improves the coulombic efficiency of lithium ion battery, and carries out selfreparing to silicium cathode material by liquid metal, avoids SEI film It is unstable, it is contacted in conjunction with liquid metal with the good interface of silicon materials and the super-low resistivity of liquid metal, realizes lithium ion The high power charging-discharging and long circulation life of battery.
Detailed description of the invention
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached Figure.
Fig. 1 is the SEM figure that liquid metal nano particle of the present invention amplifies 10000 times;
Fig. 2 is the cathode amplification 5000 that 1 liquid metal nano particle of the embodiment of the present invention and silicon nanoparticle are mixed to get SEM figure again;
Fig. 3 is the cathode amplification 10000 that 2 liquid metal nano particle of the embodiment of the present invention and micron silicon particle are mixed to get SEM figure again;
Fig. 4 is that the cathode that 3 liquid metal nano particle of the embodiment of the present invention and silicon carbide particles are mixed to get amplifies 500 times SEM figure;
Fig. 5 is that the cathode of the embodiment of the present invention 1 is assembled into lithium ion battery and carries out the curve of cycle performance test;
Fig. 6 is that the cathode of the embodiment of the present invention 1 is assembled into lithium ion battery and carries out the curve of different multiplying test;
Fig. 7 is that the cathode of the embodiment of the present invention 1 is assembled into lithium ion battery and carries out the curve of coulombic efficiency test;
Fig. 8 is the operation principle schematic diagram of liquid metal nano particle of the present invention and silicon materials interaction.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not For limiting the present invention.
Present example provides a kind of liquid metal matrix self-healing lithium cell negative pole, including negative current collector and is attached to described The negative electrode material on negative current collector surface, the negative electrode material include the composite material of liquid metal nano particle and silicon, bonding Agent;
According to mass ratio, the composite material of the liquid metal nano particle and silicon: binder=(9~90): 1;
Wherein, in the composite material of the liquid metal nano particle and silicon, the quality of liquid metal nano particle and silicon Than for 1:(1~5).
Preparation method technical solution of the invention is further explained in detail below.
The above-mentioned negative current collector of the present invention can be copper foil.
Preferably, the liquid metal nano particle is the mixture of gallium, indium, tin, and the mass ratio of the gallium, indium, tin For (6~9): (1~3): 1.Three kinds of metals of gallium indium tin have good interaction under the mixed proportion, with silicon materials, and And the volume expansion of silicon particle is utilized in chemical reaction process, cause mechanical stress to squeeze liquid metal-to-metal adhesive capsule crust, so that Silicon destroys liquid metal capsule autoxidation shell in initial lithiation, the excessive disperse of liquid metal is caused, to significantly increase Connectivity in electric conductivity and electrode microstructure, specific action principle are as shown in Figure 8.Have by liquid metal Nano capsule Self-healing properties and high capacity silicon materials between interaction so that obtain liquid metal matrix self-healing lithium cell negative pole exist When lithium ion battery is made in lithium ion battery other components, ingredient, excellent chemical property is shown.
Above-mentioned gallium, indium, tin purity be higher than 99.8% or more, avoid may cause self discharge because mixing other impurities Bring capacity attenuation is too fast.
Preferably, silicon is the active material of cathode, specifically can be nano-silicon, micron silicon, aoxidizes sub- silicon, silicon-carbon, SiOx At least one of.Under the action of aforementioned liquid metal nanoparticle, it is related to the material of silicon and the material that volume expansion is big, It can be used as negative electrode active material of the invention.
Preferably, the binder is acrylic resin, in sodium alginate, sodium carboxymethylcellulose, Kynoar It is any.These binders are the common binder of field of lithium ion battery, can be well by silicon materials, liquid metal nanometer Particle is bonded in negative current collector surface.
Liquid metal matrix self-healing lithium cell negative pole provided by the invention does not need to add additional conductive agent, but directly with Liquid metal nano particle improves the content of silicon materials, is used for lithium ion battery as self-repair material and conductive agent When upper, there is good interfacial contact and ultralow resistivity, liquid metal nano particle can carry out self to silicon materials It repairs, to realize overlength cycle characteristics, and quick charge may be implemented, high-multiplying power discharge can be carried out.
Correspondingly, the present invention also provides the preparation methods of liquid metal matrix self-healing lithium cell negative pole.In one embodiment, institute State preparation method the following steps are included:
The suspension of liquid metal nano particle is ultrasonically treated by step S01. with Si powder, is obtained liquid metal and is received The composite material of rice grain and silicon;
Step S02. disperses the composite material of binder and the liquid metal nano particle and silicon in solvent, is made The slurry of acquisition is then coated on negative current collector surface, through drying, cuts processing, obtain liquid metal matrix by slurry Self-healing lithium cell negative pole.
Detailed explanation is done to the preparation method of liquid metal matrix self-healing lithium cell negative pole below.
Specifically, in the suspension of above-mentioned liquid metal nano particle, dispersion liquid is methanol, ethyl alcohol, appointing in isopropanol One kind, these types of dispersion liquid have a good dispersion effect to liquid metal nano particle, and mix point with silicon materials It dissipates after composite material is made, also facilitates removal.
Preferably, mercaptan dispersing agent is also contained in the suspension, by the effect of mercaptan, so that liquid metal nanometer Grain dispersibility is more preferable.
Specifically, the suspension of liquid metal nano particle can be prepared using following method:
Be gallium by mass ratio: indium: tin=(6~9): (1~3): 1 gallium indium tin mixture carries out mixing place with dispersion liquid Reason, while mercaptan dispersing agent is added, and pass through Ultrasonic Pulverization, obtain the suspension of liquid metal nano particle.
When carrying out Ultrasonic Pulverization to liquid metal nano particle, ultrasonic power is not less than 400W, and ultrasonic time is not less than 20min, the temperature condition of ultrasonic treatment are 15~30 DEG C, and 5~10s of each ultrasound stands 3~5s, is ultrasonically treated 20min repeatedly Or more, it can be obtained partial size in the liquid metal nano particle suspension of 5~200nm.
Preferably, the proportion of liquid metal nano particle and dispersion liquid is 1g:(200~300 in the suspension) mL, Under the ratio, liquid metal nano particle dispersion flows are good, and are convenient for subsequent removal dispersion liquid.
In step S01, the time that the suspension of liquid metal nano particle and silicon powder are ultrasonically treated is 10~ 60min is then evaporated at 40~100 DEG C, natural cooling, can be obtained the composite material of liquid metal nano particle and silicon.
In step S02, the solvent of the composite material for dispersing binder and the liquid metal and silicon is methanol, second Any one of alcohol, isopropanol.Wherein binder is acrylic resin, sodium alginate, sodium carboxymethylcellulose, Kynoar Any one of.It is not reinflated detailed using the mixing paste technology that lithium ion battery is common, therefore herein in mixing process Thin description.
Preferably, the slurry viscosity of acquisition is 1.5 × 10-3~1.5Pas can obtain good painting under the viscosity Cover effect.
Slurry is coated on the drying process behind negative current collector surface by the present invention, is preferably dried in vacuo, vacuum drying can Effectively to avoid the generation of other side reactions.It is further preferred that 80~150 DEG C of vacuum drying temperature, the time is 6~for 24 hours.
The surface density of the negative electrode of lithium ion battery obtained as a result, is 3~5mg/cm2.Under the surface density, manufactured lithium Ion battery electrochemical performance, especially long circulation life, after reaching 1500 times, battery capacity conservation rate still can be high Up to 80% or more.
The preparation method of liquid metal matrix self-healing lithium cell negative pole of the present invention, preparation process is few, high production efficiency, Cheng Chancheng This is low, and seamless connection, easily realization industrialization can be realized with present industry line.
Since liquid metal matrix self-healing lithium cell negative pole provided by the invention has above-mentioned excellent characteristics, the present invention Furthermore provide a kind of lithium ion battery.The lithium ion battery has anode, cathode, diaphragm, electrolyte and battery case, Middle cathode is the above-mentioned liquid metal matrix self-healing lithium cell negative pole provided of the present invention, and anode, diaphragm, electrolyte and battery case are The common material of technical field of lithium ion, therefore not reinflated detailed description herein.
Lithium ion battery provided by the invention can be effective since cathode uses liquid metals base self-healing lithium cell negative pole Ground improves the coulombic efficiency of lithium ion battery, and carries out selfreparing to silicium cathode material by liquid metal, avoids SEI film It is unstable, it is contacted in conjunction with liquid metal with the good interface of silicon materials and the super-low resistivity of liquid metal, realizes lithium ion The high power charging-discharging and long circulation life of battery.
More effectively to illustrate technical solution of the present invention, technical side of the invention is illustrated below by specific embodiment Case.
Embodiment 1
A kind of preparation method of liquid metal matrix self-healing lithium electrode, comprising the following steps:
(1) preparation of gallium indium tin liquid metal nano particle isopropanol suspension:
By 0.5g purity be above 99.9% and mass ratio be gallium: indium: tin=7:2:1 gallium, indium, tin metal mixture are molten In the isopropanol of 100mL, 2.0mg mercaptan dispersing agent is added, it is still aging then in ultrasonic disintegrator ultrasonic vibration 60min 5h obtains gallium indium tin liquid metal nano particle isopropanol suspension.
(2) preparation of the composite material of liquid metal nano particle and nano silicon particles:
The gallium indium tin liquid metal nano particle isopropanol suspension and 0.5g nano-silicon powder that step (1) is obtained carry out Mixing, the average diameter 80nm of nano-silicon, the Ultrasonic Pulverization 20min at 20 DEG C in ultrasonic disintegrator, wherein every Ultrasonic Pulverization 5s, 3s is stood, ultrasonic disintegrator probe diameter 19mm, ultrasonic power 1100W fill liquid metal nano particle with nano silicon particles Divide after mixing, be evaporated at 80 DEG C, scraping residual powder obtains the composite material of liquid metal nano particle and nano silicon particles.
(3) preparation of liquid metal matrix self-healing lithium cell negative pole:
Composite material, the 0.2g10wt% of liquid metal nano particle and nano silicon particles that 0.18g step (2) is obtained Acrylic resin soln and 0.5mL isopropanol carry out mixing treatment together, for magnetic agitation to uniform slurry is obtained, slurry is viscous About 3 × 10-1Pa·s;Then slurry is poured on copper foil, is spread out slurry blade coating with 50 μm of scrapers, after natural drying It is dry to be put into vacuum oven, vacuum oven temperature sets 120 DEG C, soaking time 12h, and the pole piece after drying is cut into diameter The pole piece of 12mm is stand-by.
Embodiment 2
A kind of preparation method of liquid metal matrix self-healing lithium electrode, comprising the following steps:
(1) preparation of gallium indium tin liquid metal nano particle alcohol suspending liquid:
By 1.0g purity be above 99.9% and mass ratio be gallium: indium: tin=7:2:1 gallium, indium, tin metal mixture are molten In the ethyl alcohol of 250mL, 5.0mg mercaptan dispersing agent is added, then in ultrasonic disintegrator ultrasonic vibration 60min, still aging 5h, Obtain gallium indium tin liquid metal nano particle alcohol suspending liquid.
(2) preparation of the composite material of liquid metal nano particle and micron silicon particle:
The gallium indium tin liquid metal nano particle alcohol suspending liquid that step (1) obtains is mixed with 1.5g microns of Si powders It closes, 2 μm of the average diameter of micron silicon, the Ultrasonic Pulverization 120min at 25 DEG C in ultrasonic disintegrator, wherein every Ultrasonic Pulverization 5s, quiet 3s, ultrasonic disintegrator probe diameter 6mm, ultrasonic power 400W are set, liquid metal nano particle and micron silicon particle is sufficiently mixed It after even, is evaporated at 100 DEG C, scraping residual powder obtains the composite material of liquid metal nano particle and micron silicon particle.
(3) preparation of liquid metal matrix self-healing lithium cell negative pole:
Composite material, the 0.4g10wt% of liquid metal nano particle and micron silicon particle that 0.36g step (2) is obtained Acrylic resin soln and 1.5mL isopropanol carry out mixing treatment together, for magnetic agitation to uniform slurry is obtained, slurry is viscous About 0.5Pas;Then slurry is poured on copper foil, slurry blade coating is spread out with 50 μm of scrapers, is put into after natural drying Vacuum oven is dry, and vacuum oven temperature sets 100 DEG C, and soaking time is cut into diameter 12mm for 24 hours, by the pole piece after drying Pole piece it is stand-by.
Embodiment 3
A kind of preparation method of liquid metal matrix self-healing lithium electrode, comprising the following steps:
(1) preparation of gallium indium tin liquid metal nano particle methanol suspension:
By 2.0g purity be above 99.9% and mass ratio be gallium: indium: tin=7:2:1 gallium, indium, tin metal mixture are molten In the methanol of 500mL, 5.0mg mercaptan dispersing agent is added, it is still aging then in ultrasonic disintegrator ultrasonic vibration 100min 5h obtains gallium indium tin liquid metal nano particle methanol suspension.
(2) preparation of the composite material of liquid metal nano particle and silicon carbide particles:
The gallium indium tin liquid metal nano particle methanol suspension that step (1) obtains is mixed with 2.0g silicon-carbon powder It closes, the average grain diameter of gallium indium tin liquid metal nano particle is 1000nm, and the average diameter of silicon-carbon powder is 10 μm, in ultrasonic powder Ultrasonic Pulverization 60min at 15 DEG C in broken machine, wherein every Ultrasonic Pulverization 5s, stands 3s, ultrasonic disintegrator probe diameter 6mm, ultrasound Power 400W is evaporated at 60 DEG C after mixing well liquid metal nano particle and silicon carbide particles, and scraping residual powder obtains The composite material of liquid metal nano particle and silicon carbide particles.
(3) preparation of liquid metal matrix self-healing lithium cell negative pole:
The composite material of liquid metal nano particle and silicon carbide particles that 0.9g step (2) is obtained, 0.1g10wt% Acrylic resin soln and 0.3mL isopropanol carry out mixing treatment together, and for magnetic agitation to uniform slurry is obtained, slurry is viscous about For 1Pas;Then slurry is poured on copper foil, slurry blade coating is spread out with 100 μm of scrapers, is put into after natural drying true Empty drying box is dry, and vacuum oven temperature sets 60 DEG C, soaking time 12h, and the pole piece after drying is cut into diameter 12mm's Pole piece is stand-by.
In order to verify the microscopic appearance and other performances of the cathode that Examples 1 to 3 obtains, corresponding property is carried out to it respectively It can detect, specifically include scanning electron electron-microscope scanning (SEM) and lithium ion battery progress cycle performance, coulombic efficiency is made etc. The test of aspect.
(1) SEM is tested
According to the mode of operation that conventional SEM is scanned, specific test result is as shown in figs. 2 to 4.
Wherein, Fig. 2 is that the cathode that embodiment 1 obtains amplifies 5000 times of SEM figure, and Fig. 3 is that embodiment 2 amplifies 10000 times SEM figure, Fig. 4 be embodiment 3 amplify 500 times SEM figure.By Fig. 2~4 it is found that liquid metal respectively with silicon nanoparticle, micro- Rice silicon particle, silicon carbide particles are evenly dispersed, and pole piece structure is completely without obvious crackle.
(2) cycle performance, high rate performance and coulombic efficiency test
Half-cell is assembled with the cathode of embodiment 1 and metal lithium sheet, is 8A/g's in current density after button cell is made Under the conditions of carry out charge-discharge test with the test of, different multiplying and coulombic efficiency test, test result is as shown in Fig. 5,6,7.
As can be seen from Figure 5, the half-cell assembled has the electrochemistry circulating ring number of overlength, can protect after 200 circle circulations 90% or more capacity is held, and still there is 82% capacity retention ratio after 1500 charge and discharge electric circles circulation.Illustrate the present invention The cathode that embodiment 1 obtains can effectively mention the cycle performance of battery, and as can be known from Fig. 6, battery has the forthright again of superelevation Can, in 20A g-1When be 360mAh g-1, fully charged in 65 seconds/electric discharge has ultrafast charge-discharge performance.As can be seen from Figure 7 Since liquid metal is during silicon particle expands, the stress by silicon particle is squeezed, and destroys liquid metal particle Insulation sheath, the liquid metal outflow disperse with high conductivity and high fluidity for being is around silicon particle, spontaneous realization Liquid metal conductive network and can the problem of Cracking that occurs in cyclic process of spontaneous reparation silicon, and at the same time liquid metal pair The gap of silicon particle cluster realizes preferable filling and cladding, the area of exposure in the electrolytic solution is reduced, to reduce The increment of SEI film, the coulombic efficiency for improving first circle and then recycling.
Since the cathode performance that preparation method of the invention obtains is stablized, homogeneity is good, therefore does not carry out to embodiment 2,3 Corresponding electrochemical property test.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc. within mind and principle should all include within protection scope of the present invention.

Claims (9)

1. a kind of liquid metal matrix self-healing lithium cell negative pole including negative current collector and is attached to the negative current collector surface Negative electrode material, which is characterized in that the negative electrode material includes the composite material of liquid metal nano particle and silicon, binder;
According to mass ratio, the composite material of the liquid metal nano particle and silicon: binder=(9~90): 1;
Wherein, in the composite material of the liquid metal nano particle and silicon, the mass ratio of liquid metal nano particle and silicon is 1:(1~5).
2. liquid metal matrix self-healing lithium cell negative pole as described in claim 1, which is characterized in that the liquid metal nanometer Grain is the mixture of gallium, indium, tin, and the mass ratio of the gallium, indium, tin is (6~9): (1~3): 1.
3. liquid metal matrix self-healing lithium cell negative pole as described in claim 1, which is characterized in that the silicon is nano-silicon, micro- Rice silicon aoxidizes sub- silicon, silicon-carbon, SiOxAt least one of.
4. liquid metal matrix self-healing lithium cell negative pole as described in claim 1, which is characterized in that the binder is acrylic acid Any one of resin, sodium alginate, sodium carboxymethylcellulose, Kynoar.
5. such as the preparation method of the described in any item liquid metal matrix self-healing lithium cell negative poles of Claims 1 to 4, feature exists In at least including the following steps:
The suspension of liquid metal nano particle is ultrasonically treated by step S01. with Si powder, obtains liquid metal nanometer The composite material of grain and silicon;
Step S02. disperses the composite material of binder and the liquid metal nano particle and silicon in solvent, and slurry is made The slurry of acquisition is then coated on negative current collector surface, through drying, cuts processing by material, obtains liquid metal matrix certainly Heal lithium cell negative pole.
6. the preparation method of liquid metal matrix self-healing lithium cell negative pole as claimed in claim 5, which is characterized in that the liquid The dispersion liquid of the suspension of metal nanoparticle is any one of methanol, ethyl alcohol, isopropanol, contains mercaptan in the suspension Dispersing agent, the proportion of liquid metal nano particle and dispersion liquid is 1g:(200~300 in the suspension) mL.
7. the preparation method of liquid metal matrix self-healing lithium cell negative pole as claimed in claim 5, which is characterized in that the solvent For any one of methanol, ethyl alcohol, isopropanol;And/or the viscosity of the slurry is 1.5 × 10-3~1.5Pas.
8. a kind of lithium ion battery, including anode, cathode, diaphragm, electrolyte and battery case, which is characterized in that the cathode is The described in any item liquid metal matrix self-healing lithium cell negative poles of Claims 1 to 4 or the cathode use such as claim 5 The preparation method of~7 described in any item liquid metal matrix self-healing lithium cell negative poles is prepared.
9. lithium ion battery as claimed in claim 8, which is characterized in that the surface density of the negative electrode of lithium ion battery be 3~ 5mg/cm2
CN201810544833.2A 2018-05-31 2018-05-31 Liquid metal matrix self-healing lithium cell negative pole and preparation method and lithium ion battery Pending CN110061190A (en)

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CN110518278A (en) * 2019-08-19 2019-11-29 南方科技大学 Solid electrolyte and preparation method and solid state battery with cathode interface layer
CN112420978B (en) * 2019-08-22 2022-12-09 比亚迪股份有限公司 Composite negative electrode, solid-state lithium battery and preparation method of solid-state lithium battery
CN112420978A (en) * 2019-08-22 2021-02-26 比亚迪股份有限公司 Composite negative electrode, solid-state lithium battery and preparation method of solid-state lithium battery
CN110911689A (en) * 2019-10-31 2020-03-24 南方科技大学 Current collector and preparation method thereof, electrode plate and secondary battery
CN111668450A (en) * 2020-06-22 2020-09-15 吉林大学 Paper-based aluminum air battery with liquid alloy modified anode and preparation method
CN111682182A (en) * 2020-06-22 2020-09-18 吉林大学 Printable's novel flexible paper base aluminium air battery
CN111682182B (en) * 2020-06-22 2021-09-21 吉林大学 Printable's novel flexible paper base aluminium air battery
CN113594440A (en) * 2021-07-08 2021-11-02 天津大学 Lithium ion battery cathode material with multilevel conductive structure and preparation method thereof
CN113594440B (en) * 2021-07-08 2023-07-18 天津大学 Lithium ion battery anode material with multistage conductive structure and preparation method thereof
CN113555527A (en) * 2021-07-21 2021-10-26 珠海冠宇电池股份有限公司 Negative plate and lithium ion battery
CN113991194A (en) * 2021-10-29 2022-01-28 山东大学 Liquid metal modified two-dimensional siloxene cathode and preparation method and application thereof
CN113991194B (en) * 2021-10-29 2023-08-15 山东大学 Liquid metal modified two-dimensional siloxanene negative electrode and preparation method and application thereof
CN114039026A (en) * 2021-11-02 2022-02-11 远景动力技术(江苏)有限公司 Cathode material for solid lithium ion battery and preparation method and application thereof
CN114242931A (en) * 2021-11-12 2022-03-25 欣旺达电动汽车电池有限公司 Method for improving battery cell pole piece and performance

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Application publication date: 20190726