CN114388739B - Composite lithium metal cathode, preparation method and application - Google Patents
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Abstract
The invention relates to a composite lithium metal cathode, a preparation method and application. The composite lithium metal negative electrode is internally provided with materials with different lithium ion conductivities and conductive materials, wherein the material with low lithium ion conductivity is used as a lithium ion insulating layer and used for preventing electrochemical precipitation of lithium ions to the positive electrode direction during charging, inhibiting the volume expansion of the negative electrode and preventing the short circuit of a battery; the structure can improve the cycle life and safety of the lithium metal battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a composite lithium metal negative electrode, a preparation method and application.
Background
The theoretical specific capacity of the graphite is only 372 mA h g-1The energy density of the lithium ion battery taking graphite as the negative electrode is limited, and the theoretical specific capacity of lithium metal can reach 3860 mA h g-1The lithium ion battery has a theoretical specific capacity which is more than 10 times that of graphite, and can greatly improve the energy density of the battery once being commercialized as a negative electrode material, but lithium metal is used as a negative electrode material, is an electron transport channel and an active substance, and lithium ions can obtain electrons from the lithium metal at a solid electrolyte interface film (SEI film and lithium ion transport channel) and a lithium metal interface to be changed into lithium atoms in a charging process, and are electrochemically precipitated on the surface of the lithium metal. Because the contact between lithium metal and the SEI film is unstable and the SEI film has uneven component distribution, the electrochemical behavior of lithium atoms on the surface of the lithium metal is uncontrollable, lithium dendrites are easily formed, the SEI film can be punctured by the lithium dendrites, the cycle life is reduced, and the SEI film can be punctured by the lithium dendrites along with the growth of the dendrites, even a diaphragm can be punctured, short circuits can be caused, and safety occursAnd (4) solving the overall problem.
Disclosure of Invention
The invention provides a composite lithium metal negative electrode, a preparation method and application, and aims to solve the problems of low coulombic efficiency and safety caused by lithium dendrites in a lithium metal negative electrode.
In a first aspect, the present application provides a composite lithium metal negative electrode, which is composed of a lithium ion insulating layer, an electron transport channel and a lithium ion transport channel, wherein the lithium ion insulating layer is composed of an inorganic substance or an organic substance having low lithium ion conductivity, the lithium ion transport channel is composed of a polymer having high lithium ion conductivity and high entropy elasticity or a mixture of a polymer having high entropy elasticity and an inorganic ceramic having high lithium ion conductivity, and the electron transport channel is composed of a framework of a metal microporous array. The lithium ion insulating layer covers the surface of the metal micropore array, the lithium ion transmission channel has high entropy elasticity, and the metal micropores can be filled, so that the lithium ion transmission channel and the electron transmission channel are kept in good contact;
specifically, the principle of the invention for improving the electrochemical performance of the lithium metal negative electrode is as follows: the lithium ion transmission channel is compressed by the newly formed lithium metal layer along with the progress of electrochemical reaction, the volume is reduced, the entropy elasticity is increased, the lithium ion transmission channel has high entropy elasticity, so that the lithium ion transmission channel and the electron transmission channel are always kept in good contact, thereby inducing the uniform electrochemical precipitation of lithium ions and inhibiting the growth of lithium dendrites, during discharging, the lithium atoms on the surface of the lithium metal layer escape from the lattice surface into the lithium ion transmission channel, the volume of the lithium metal layer is reduced, and the volume of the lithium ion transmission channel is enlarged, the entropy elasticity is reduced, the lithium ion transmission channel and the electron transmission channel are always kept in good contact through the entropy elasticity, so that the electrochemical process has good dynamic performance, the lithium ion insulating layer is arranged on the surface of the metal micropore array, the lithium ions are prevented from being electrochemically precipitated on the surface of the array, the lithium ions are prevented from being electrochemically precipitated towards the positive electrode, the volume expansion of the negative electrode can be inhibited, and the short circuit phenomenon is avoided;
in a second aspect, the present application provides a method for preparing a composite lithium metal negative electrode, comprising the steps of:
(1) adding the polymer with high crystallinity into an organic solvent, and magnetically stirring for a plurality of hours at normal temperature to fully dissolve the polymer with high crystallinity into the organic solvent to obtain the organic solvent containing the polymer with high crystallinity;
(2) uniformly coating the organic solvent containing the high-crystallinity polymer obtained in the step (1) on the surface of a metal sheet under the conditions that the water content is less than or equal to 0.01ppm and the oxygen content is less than or equal to 0.01ppm, drying the metal sheet in a vacuum drying oven at a certain temperature for 36 hours, and obtaining the metal sheet covered with the high-crystallinity polymer along with the volatilization of the organic solvent;
(3) punching the metal sheet covered with the high-crystallinity polymer obtained in the step (2) by using a laser under a certain wavelength to form a polymer-metal sheet composite micron hole array, wherein the skeleton of the metal sheet micron hole array is used as an electron transmission channel, and the high-crystallinity polymer is used as a lithium ion insulating layer;
(4) adding the polymer with high entropy elasticity into an organic solvent, and magnetically stirring for a plurality of hours at normal temperature to fully dissolve the polymer with high entropy elasticity into the organic solvent to obtain the organic solvent containing the polymer with high entropy elasticity;
(5) adding an inorganic solid electrolyte into the organic solvent containing the high-entropy elastic polymer obtained in the step (4), stirring for a plurality of hours at a certain temperature under the conditions that the water content is less than or equal to 0.01ppm and the oxygen content is less than or equal to 0.01ppm to obtain an organic solvent containing the inorganic solid electrolyte and the high-entropy elastic polymer, then coating the organic solvent on the surface of the polymer-metal sheet composite micropore array obtained in the step (3), filling the liquid inorganic solid electrolyte and the organic solvent of the high-entropy elastic polymer into silver micropores, then placing the silver micropores in a vacuum drying oven, drying for a plurality of hours at a certain temperature in vacuum, and volatilizing the organic solvent to obtain a composite lithium metal negative electrode material without lithium;
(6) cutting the lithium-free lithium metal negative electrode material obtained in the step (5) into a plate shape, forming a half battery with metal lithium, and then carrying out electrochemical lithium plating on the lithium-free composite lithium metal negative electrode material for a plurality of hours under a certain current density to obtain a composite lithium metal negative electrode material containing metal lithium (the composite lithium metal negative electrode material in a fully charged state);
optionally, the lithium ion insulating layer is composed of a polymer with a crystallinity of ≧ 50%;
optionally, the lithium ion transport channel consists of a mixture of a high entropy elastic polymer electrolyte with crystallinity ≦ 10% and a sulfide solid electrolyte;
alternatively, the organic solvent is Tetrahydrofuran (THF);
optionally, the electron transport channel is composed of a silver micro-pore array skeleton;
in a third aspect, the present application provides the use of a composite lithium metal negative electrode for lithium metal solid state batteries and lithium metal liquid state batteries.
The beneficial effect of this application does: according to the invention, the lithium ion insulating layer, the electron transmission channel and the lithium ion transmission channel are constructed in the lithium metal negative electrode, the direction of electrochemical precipitation of lithium ions is adjusted through different lithium ion conduction capacities of different substances, the growth of lithium dendrites to the positive electrode direction is inhibited, the occurrence of short circuit is prevented, and the good electrochemical dynamic performance in the electrode is ensured through the stable contact of the lithium ion transmission channel with high entropy elasticity and the electron transmission framework, so that the lithium ion battery has longer cycle life and higher safety.
Drawings
Fig. 1 is a schematic view of the structure of a composite lithium metal negative electrode in a non-electrical state according to the present invention.
Icon: 100-a lithium ion insulating layer; 200-electron transport channels; 300-lithium ion transport channel.
Fig. 2 is a schematic structural view of the composite lithium metal negative electrode in a full charge state according to the present invention.
Icon: 100-a lithium ion insulating layer; 200-electron transport channels; 300-lithium ion transport channel, 400-metallic lithium.
Fig. 3 is a partial structural view of the lithium composite metal negative electrode in the electroless state.
Icon: 301-high entropy elastic organic polymers, 302-inorganic solid electrolytes.
Fig. 4 is a partial structural view of the lithium composite metal negative electrode in a charged state.
Icon: 301-high entropy elastic organic polymers; 302-inorganic solid electrolyte; 400-lithium metal.
Fig. 5 is a partial structural view of the lithium composite metal negative electrode in a full charge state.
An icon: 301-high entropy elastic organic polymers; 302-inorganic solid electrolyte; 400-lithium metal.
It should be understood that the above-described figures are merely schematic and are not drawn to scale.
Detailed Description
The embodiment provides a composite lithium metal negative electrode, which comprises a lithium ion insulating layer 100, an electron transmission channel 200 and a lithium ion transmission channel 300, wherein the lithium ion insulating layer 100 has a lithium ion conductivity ≦ 1 × 10-4 mS cm-1The lithium ion transmission channel 300 is composed of inorganic matters or organic matters, and the lithium ion conductivity is not less than 1 mS cm-1The entropy elastic modulus of the polymer is 1-200N cm-2Polymer (b) and lithium ion conductivity ≧ 1X 102 mS cm-1The electron transport channel 200 is composed of a skeleton of a metal micro-pore array, the lithium ion insulating layer 100 covers the surface of the metal micro-pore array, the lithium ion transport channel 300 has high entropy elasticity, and the metal micro-pores are filled so that the lithium ion transport channel 300 is in contact with the electron transport channel 200.
Optionally, the lithium ion conductivity of the lithium ion transmission channel is ≧ 1 mS cm-1(ii) a The thickness of the lithium ion transmission channel is 1 to100 μm. The lithium ion conductivity of the lithium ion insulating layer is less than or equal to 1 x10-4 mS cm-1(ii) a The lithium ion insulating layer is composed of a polymer with high crystallinity, the high crystallinity is greater than or equal to 50% in crystallinity, and the thickness of the lithium ion insulating layer is 0.5-50 [ mu ] m. The electronic transmission channel has the conductivity of ≧ 1 × 108 mS cm-1The metal composition of (a); the electronic transmission channel is composed of a silver micropore array framework, and the thickness of the electronic transmission channel is 1-100 mu m. The volume of the lithium ion transmission channel becomes smaller in the process of charging the battery and becomes larger in the process of discharging the battery.
As another exemplary embodiment, the composite lithium metal negative electrode may be applied to a lithium metal solid-state battery and a lithium metal liquid-state battery.
As another exemplary embodiment, the method of preparing the composite lithium metal anode is as follows:
(1) adding 1g of Butadiene Rubber (BR) into 100 ml of Tetrahydrofuran (THF), and magnetically stirring at normal temperature for 12 hours to fully dissolve the BR into the THF to obtain a THF solution containing the BR;
(2) uniformly coating the THF solution containing BR obtained in the step (1) on the surface of a silver (Ag) foil with the thickness of 20 mu m under the conditions that the water content is less than or equal to 0.01ppm and the oxygen content is less than or equal to 0.01ppm, then drying the silver (Ag) foil in a vacuum drying oven at the temperature of 30 ℃ for 36 hours, after THF is completely volatilized, covering one surface of the Ag foil with a layer of cis-Butadiene Rubber (BR) film, wherein the BR film with the thickness of 1 mu m is used as a lithium ion insulating layer 100 because the BR has high crystallinity;
(3) and (3) punching the Ag foil covered with the BR film on the surface obtained in the step (2) by using a YT-cx100 laser and a laser with a wavelength of 1064 nm, wherein the diameter of the holes is 100 mu m, and the space distance is 20 mu m, so that a silver Ag micron hole array (BR-Ag) covered with a BR layer is obtained. An Ag framework of BR-Ag is used as an electron transmission channel 200, and a BR film is used as a lithium ion insulating layer 100;
(4) adding 1g of BR into 100 ml of THF, and magnetically stirring for 12 hours at normal temperature to fully dissolve the BR into the THF to obtain a THF solution containing the BR;
(5) water content is less than or equal to 0.01ppm, oxygenUnder the condition that the content is less than or equal to 0.01ppm, 0.6 g of Li5.5PS4.5Cl1.5Adding the solution into the THF solution containing BR obtained in the step (4), and stirring the solution for a plurality of hours at the temperature of 30 ℃ to obtain the solution containing Li5.5PS4.5Cl1.5And BR in THF solution, then coating the BR-Ag surface obtained in step (3) with the liquid state containing Li5.5PS4.5Cl1.5And BR is filled into Ag micropores in a THF solution, then the Ag micropore array is dried in a vacuum drying oven at the temperature of 30 ℃ for 48 hours, THF is volatilized, and Li with uniform distribution in the interior is obtained5.5PS4.5Cl1.5Solid BR (BR-LPSCl) in the form of particles, BR being a high-entropy elastic organic polymer 301, Li5.5PS4.5Cl1.5As the inorganic solid electrolyte 302. BR-LPSCl is used as a lithium ion transmission channel 300, and finally, the step is carried out to obtain a lithium-free composite lithium metal negative electrode material (BR-Ag-LPSCl);
(6) cutting the lithium-free composite lithium metal negative electrode material obtained in the step (5) into a plate shape, forming a half cell with metal lithium, and then performing lithium ion plating at 0.2 mA cm-2Electrochemically plating lithium to the lithium-free composite lithium metal negative electrode material for 50 hours under the current density to obtain the lithium-free composite lithium metal negative electrode material with the unit area capacity of 10 mA h cm-2A composite lithium metal negative electrode material (BR-Ag-LPSCl-Li) of metal lithium (a composite lithium metal negative electrode in a full-charge state);
referring to FIGS. 1 and 2, the BR film as the Li-ion insulation layer 100 has a thickness of 0.5-50 μm and an entropy elasticity modulus of 10-50N cm-2To (c) to (d);
referring to FIG. 1, a silver micron pore framework serving as an electron transmission channel 200 is 1-100 mu m thick and has good conductivity and mechanical property, the diameter of the silver micron pore is 100-1000 mu m, and the thickness of the silver micron pore is 1-100 mu m;
referring to fig. 1 and 2, BR-LPSCl is filled in the silver micro-holes as the lithium ion transport channels 300;
referring to fig. 2, the metal lithium 400 is electroplated between the Ag micro-pore wall and BR-LPSCl by electroplating, and as the metal lithium 400 increases, BR-LPSCl acts as the lithium ion transport channel 300, and the volume is reduced;
referring to fig. 3, fig. 3 is a partial structure diagram of the composite lithium metal negative electrode in the electroless state, wherein the grid 301 is a schematic diagram of BR, and the diamond-shaped black particles 302 are a schematic diagram of LPSCl;
referring to fig. 4, fig. 4 is a partial structural view of a lithium composite metal negative electrode in a charged state, a grid 301 is a schematic view of BR, diamond-shaped black particles 302 are a schematic view of LPSCl, and circular black particles 400 are a schematic view of lithium metal. As charging progresses, the lithium metal volume increases and the lithium ion transport channel volume decreases;
referring to fig. 5, fig. 5 is a partial structure diagram of the composite lithium metal negative electrode in a full charge state, where a grid 301 is a schematic diagram of BR, a diamond-shaped black particle 302 is a schematic diagram of LPSCl, and a circular black particle 400 is a schematic diagram of lithium metal, and in the full charge state, the lithium metal volume is maximized and the lithium ion transport channel volume is minimized.
Claims (7)
1. A composite lithium metal anode characterized by:
the lithium ion battery comprises a lithium ion insulating layer, an electron transmission channel and a lithium ion transmission channel, wherein the lithium ion insulating layer has a lithium ion conductivity of ≦ 1 × 10-4 m S cm-1The lithium ion transmission channel consists of lithium ion conductivity ≧ 1 mS cm-1The entropy elastic modulus of the polymer is 1-200N cm-2Polymer (b) and lithium ion conductivity ≧ 1X 102 mS cm-1The electron transport channel is composed of a framework of a metal micropore array, the lithium ion insulating layer covers the surface of the metal micropore array, and the lithium ion transport channel fills the metal micropores and is in contact with the electron transport channel.
2. A composite lithium metal anode according to claim 1, wherein:
the lithium ion conductivity of the lithium ion transmission channel is not less than 1 mS cm-1(ii) a The thickness of the lithium ion transmission channel is 1-100 mu m.
3. A composite lithium metal anode according to claim 1, wherein:
the lithium ion conductivity of the lithium ion insulating layer is less than or equal to 1 x10-4 m S cm-1(ii) a The lithium ion insulating layer is composed of a polymer with high crystallinity, the high crystallinity is greater than or equal to 50% in crystallinity, and the thickness of the lithium ion insulating layer is 0.5-50 [ mu ] m.
4. A composite lithium metal anode according to claim 1, wherein:
the electronic transmission channel has the conductivity of ≧ 1 × 108 mS cm-1The metal composition of (a); the electronic transmission channel is composed of a silver micropore array framework, and the thickness of the electronic transmission channel is 1-100 mu m.
5. A composite lithium metal anode according to claim 1, wherein:
the volume of the lithium ion transmission channel becomes smaller in the process of charging the battery and becomes larger in the process of discharging the battery.
6. Use of a composite lithium metal negative electrode according to claim 1, wherein:
the composite lithium metal negative electrode is applied to lithium metal solid batteries and lithium metal liquid batteries.
7. The preparation method of the composite lithium metal negative electrode is characterized by comprising the following steps of:
(1) adding a polymer with the crystallinity of not less than 50% into an organic solvent, and performing magnetic stirring at normal temperature for not less than 6 hours to fully dissolve the polymer into the organic solvent, thereby obtaining the organic solvent containing the polymer with the crystallinity of not less than 50%; the organic solvent is one or more of tetrahydrofuran, N-methyl pyrrolidone and N, N-dimethylformamide;
(2) uniformly coating the organic solvent containing the polymer with the crystallinity of more than or equal to 50% obtained in the step (1) on the surface of a metal sheet under the conditions that the water content is less than or equal to 0.01ppm and the oxygen content is less than or equal to 0.01ppm, then drying the metal sheet in a vacuum drying oven at the temperature of 60 ℃ for more than or equal to 12 hours, and obtaining the metal sheet covered with the polymer with the crystallinity of more than or equal to 50% along with the volatilization of the organic solvent;
(3) punching the metal sheet covered with the polymer with the crystallinity being larger than or equal to 50% obtained in the step (2) by using laser to form a polymer-metal sheet composite micron hole array, wherein a framework of the metal sheet micron hole array is used as an electronic transmission channel, the polymer with the crystallinity being larger than or equal to 50% is used as a lithium ion insulating layer, the laser wavelength is 100-10000 nm, and the laser is emitted by a laser;
(4) the conductivity of lithium ion is ≧ 1 mS cm-1The sum entropy elastic modulus is 1-200N cm-2Adding the polymer into an organic solvent, and stirring for ≧ 6 hours under magnetic force at normal temperature to fully dissolve the polymer into the organic solvent, thereby obtaining a lithium ion-containing polymer with a conductivity of ≧ 1 mS cm-1The sum entropy elastic modulus is 1-200N cm-2An organic solvent for the polymer of (1);
(5) adding an inorganic solid electrolyte into the lithium ion-containing conductivity ≧ 1 mS cm obtained in the step (4)-1The sum entropy elastic modulus is 1-200N cm-2The polymer of (1) is stirred at room temperature for 2 hours under the conditions that the water content is not more than 0.01ppm and the oxygen content is not more than 0.01ppm to obtain a polymer containing an inorganic solid electrolyte and having a lithium ion conductivity of not less than 1 mS cm-1The sum entropy elastic modulus is 1-200N cm-2Coating the organic solvent of the polymer on the surface of the polymer-metal sheet composite micron pore array obtained in the step (3), filling the liquid inorganic solid electrolyte and the organic solvent of the polymer into silver micron pores, drying the silver micron pore array in a vacuum drying oven at 60 ℃ for not less than 8 hours, and volatilizing the organic solvent to obtain a lithium-free compositeA lithium-containing metal negative electrode material;
(6) forming a half cell by the lithium metal and the lithium-free composite lithium metal negative electrode material obtained in the step (5), and then electrochemically plating lithium on the lithium-free composite lithium metal negative electrode material with the surface capacity of 10-100 mA h cm-2And obtaining the composite lithium metal negative electrode material containing the metal lithium.
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| CN112968174A (en) * | 2021-02-23 | 2021-06-15 | 电子科技大学 | Lithium-philic alloy modification layer, composite lithium negative electrode material, and preparation methods and applications of lithium-philic alloy modification layer and composite lithium negative electrode material |
| CN113140812A (en) * | 2021-03-04 | 2021-07-20 | 恒大新能源技术(深圳)有限公司 | Lithium metal negative electrode, preparation method thereof and lithium secondary battery |
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