CN110635113A - Lithium cathode or sodium cathode, and preparation method and application of lithium cathode or sodium cathode - Google Patents
Lithium cathode or sodium cathode, and preparation method and application of lithium cathode or sodium cathode Download PDFInfo
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Abstract
The invention relates to the technical field of lithium/sodium batteries, and particularly provides a lithium cathode or a sodium cathode, and a preparation method and application of the lithium cathode or the sodium cathode. The preparation method comprises the steps of coating the molten anti-perovskite solid electrolyte on the surface of a current collector so as to form a layer of anti-perovskite solid electrolyte film on the surface of the current collector; depositing lithium or sodium on the surface of the current collector by adopting an electrochemical method to obtain a lithium cathode or a sodium cathode; or the anti-perovskite solid electrolyte is deposited on the surface of the lithium metal sheet or the sodium metal sheet in a magnetron sputtering mode, an anti-perovskite solid electrolyte membrane is obtained on the surface of the lithium/sodium metal sheet, and a lithium cathode or a sodium cathode is obtained. The invention forms a layer of anti-perovskite solid electrolyte film on the surface of the lithium cathode or the sodium cathode, the anti-perovskite solid electrolyte film is used as an artificial solid electrolyte film, has high lithium ion or sodium ion conductivity, and inhibits the generation of lithium/sodium dendrite, thereby improving the electrochemical performance of the lithium/sodium battery.
Description
Technical Field
The invention belongs to the technical field of lithium/sodium batteries, and particularly relates to a lithium cathode or a sodium cathode, and a preparation method and application of the lithium cathode or the sodium cathode.
Background
The theoretical specific capacity of the graphite negative electrode material used by the current commercial lithium battery is only 372mAh/g, and the application requirement of a novel high-energy-density lithium battery is difficult to meet. The specific capacity of the metallic lithium is 3860mAh g-1The reduction potential is-3.040V, and the density is 0.534g/cm3And at the same time, is flexible and therefore is considered to be an extremely competitive next-generation high energy density secondary battery anode material, called "holy grail" for lithium batteries. However, lithium dendrites are very easy to grow in the charging and discharging processes of the lithium metal negative electrode, and on one hand, the lithium dendrites may puncture a diaphragm and contact with the positive electrode to cause short circuit in the battery, so that thermal failure is generated, and risks such as spontaneous combustion or explosion are caused; on the other hand, the lithium dendrite structure is loose and porous, and is easy to fall off to form dead lithium without electrochemical activity, and the capacity is lost. In addition, the specific surface area of the negative electrode is increased due to the growth of lithium dendrites, and a large amount of electrolyte is consumed to form a solid electrolyte membrane, resulting in the degradation of the capacity and the reduction of the cycle life of the battery. Therefore, the problem of lithium dendrite growth has severely hindered the commercial application of new generation high energy density secondary lithium metal batteries such as lithium sulfur batteries, lithium air batteries, etc. For sodium ion batteries, the cost is greatly reduced compared to lithium ion batteries, but the development is limited due to the same problem of sodium dendrites.
Disclosure of Invention
The invention provides a preparation method of a lithium negative electrode or a sodium negative electrode and the lithium negative electrode or the sodium negative electrode, aiming at the problems that the lithium dendrite existing in the lithium battery and the sodium dendrite existing in the sodium battery cause the rapid capacity attenuation and the influenced cycle life of the lithium battery and the sodium battery.
Further, a lithium battery including the lithium negative electrode and a sodium battery including the sodium negative electrode are also provided.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method of making a lithium or sodium anode comprising the steps of:
providing an anti-perovskite solid electrolyte, melting the anti-perovskite solid electrolyte, and coating the melted anti-perovskite solid electrolyte on the surface of a current collector so as to form a layer of anti-perovskite solid electrolyte film on the surface of the current collector;
depositing lithium or sodium on the surface of the current collector by adopting an electrochemical method to obtain a lithium cathode or a sodium cathode;
alternatively, the first and second electrodes may be,
and depositing the anti-perovskite solid electrolyte on the surface of a lithium metal sheet or a sodium metal sheet in a magnetron sputtering mode, so as to form a layer of anti-perovskite solid electrolyte membrane on the surface of the lithium metal sheet or the sodium metal sheet, and thus obtaining the lithium cathode or the sodium cathode.
Correspondingly, the lithium negative electrode or the sodium negative electrode comprises a current collector, a lithium metal layer stacked on the surface of the current collector, and an anti-perovskite solid electrolyte membrane stacked on the surface of the lithium metal layer; or the lithium negative electrode comprises a lithium metal sheet and an anti-perovskite solid electrolyte membrane coated on the surface of the lithium metal sheet;
the sodium negative electrode comprises a current collector, a sodium metal layer stacked on the surface of the current collector, and an anti-perovskite solid electrolyte membrane stacked on the surface of the sodium metal layer; or the sodium negative electrode comprises a sodium metal sheet and an anti-perovskite solid electrolyte membrane coated on the surface of the sodium metal sheet.
Further, the lithium battery is a lithium-sulfur battery and comprises a lithium negative electrode, and the lithium negative electrode is the lithium negative electrode.
A sodium battery comprises a sodium negative electrode, wherein the sodium negative electrode is the sodium negative electrode.
The invention has the technical effects that:
compared with the prior art, the preparation method of the lithium cathode or the sodium cathode obtains the lithium cathode or the sodium cathode with the anti-perovskite solid electrolyte membrane in an electrochemical or magnetron sputtering mode, and forms a stable artificial solid electrolyte membrane (SEI) on the surface of the lithium cathode or the sodium cathode directly.
According to the lithium cathode or the sodium cathode, the surface of the lithium cathode or the sodium cathode is provided with the anti-perovskite solid electrolyte membrane which is used as an artificial solid electrolyte membrane (SEI) and has high lithium ion or sodium ion conductivity, so that the anti-perovskite solid electrolyte membrane plays a role of a fast ion transfer conductor when the lithium cathode or the sodium cathode is assembled into a battery and is charged and discharged, and meanwhile, the anti-perovskite solid electrolyte membrane is used as the artificial SEI membrane, so that other anions in electrolyte adsorbed around the lithium ions or the sodium ions can be prevented from entering the cathode, desolvation of the lithium ions or the sodium ions is realized, meanwhile, the anti-perovskite solid electrolyte membrane is beneficial to lithium fluoride in the lithium battery, and is beneficial to uniform deposition of lithium, the generation of lithium dendrites is reduced or even avoided, and the electrochemical performance of the; the method is favorable for the generation of sodium fluoride in the sodium battery, promotes the uniform deposition of sodium, reduces or even inhibits the generation of sodium dendrite, and is favorable for improving the electrochemistry of the sodium battery.
The lithium battery provided by the invention is a lithium-sulfur battery, and the surface of a lithium cathode of the lithium-sulfur battery is provided with a layer of anti-perovskite solid electrolyte membrane, so that the branch crystallization of lithium metal can be inhibited, the electrochemical performance of the lithium battery is further improved, and particularly the cycle life of the lithium-sulfur battery can be prolonged.
According to the sodium battery provided by the invention, the surface of the sodium cathode is provided with the layer of the anti-perovskite solid electrolyte film, so that the branch crystallization of sodium metal can be inhibited, the electrochemical performance of the sodium battery is further improved, and particularly the cycle life of the sodium battery can be prolonged.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an XRD diffraction line of an anti-perovskite solid electrolyte prepared in example 1 of the present invention;
FIG. 2 is an SEM photograph of example 1 of the present invention after coating an anti-perovskite solid electrolyte on a copper foil;
FIG. 3 is an elemental analysis chart of example 1 of the present invention after coating an anti-perovskite solid electrolyte on a copper foil;
FIG. 4 is an elemental analysis chart of example 1 of the present invention after coating an anti-perovskite solid electrolyte on a copper foil;
FIG. 5 is an elemental analysis chart of example 1 of the present invention after coating an anti-perovskite solid electrolyte on a copper foil;
FIG. 6 is an SEM image of a disassembled lithium negative electrode of a lithium sulfur battery of example 1 of the present invention after cycling;
FIG. 7 is an SEM image of a disassembled lithium negative electrode of a lithium sulfur battery of example 1 of the present invention after cycling;
FIG. 8 is an SEM image of a disassembled lithium negative electrode of a lithium sulfur battery of comparative example 1 according to the present invention after cycling;
FIG. 9 is an SEM image of a disassembled lithium negative electrode of a lithium sulfur battery of comparative example 1 according to the present invention after cycling;
FIG. 10 is a graph showing the cycle profiles of lithium sulfur batteries obtained in example 1 of the present invention and comparative example 1;
FIG. 11 is a graph showing the cycle profiles of lithium sulfur batteries obtained in example 2 of the present invention and comparative example 2;
fig. 12 is a cycle curve diagram of a sodium-sulfur battery prepared in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a lithium negative electrode or a sodium negative electrode. The method for preparing the lithium negative electrode or the sodium negative electrode is a method for preparing the lithium negative electrode or a method for preparing the sodium negative electrode, and the lithium negative electrode and the sodium negative electrode are explained together because the lithium negative electrode and the sodium negative electrode are prepared by the same process except for the difference of lithium and sodium materials.
The preparation method of the lithium negative electrode or the sodium negative electrode comprises the following steps:
providing an anti-perovskite solid electrolyte, then carrying out melting treatment on the anti-perovskite solid electrolyte to obtain a molten anti-perovskite solid electrolyte, and coating the molten anti-perovskite solid electrolyte on the surface of a current collector so as to form a layer of anti-perovskite solid electrolyte membrane on the surface of the current collector;
lithium metal or sodium metal is deposited on the surface of the current collector with the anti-perovskite solid electrolyte membrane on the surface by adopting an electrochemical method to obtain a lithium cathode or a sodium cathode, the lithium cathode structure obtained by the method is 'anti-perovskite solid electrolyte membrane-lithium metal layer-current collector', and the sodium cathode structure obtained by the method is 'anti-perovskite solid electrolyte membrane-sodium metal layer-current collector', and is all of a sandwich structure.
Alternatively, the above method for producing a lithium negative electrode or a sodium negative electrode may include the steps of:
providing an anti-perovskite solid electrolyte, and then depositing the anti-perovskite solid electrolyte on the surface of a lithium metal sheet or a sodium metal sheet by adopting a magnetron sputtering mode, so as to form a layer of anti-perovskite solid electrolyte film on the surface of the lithium metal sheet or the sodium metal sheet, and thus obtaining a lithium negative electrode or a sodium negative electrode, wherein the structure of the obtained lithium negative electrode is 'anti-perovskite solid electrolyte film-lithium metal sheet-anti-perovskite solid electrolyte film', and the structure of the sodium negative electrode is 'anti-perovskite solid electrolyte film-sodium metal sheet-anti-perovskite solid electrolyte film'.
Whether an electrochemical deposition method or a magnetron sputtering method is adopted, when the prepared cathode is a lithium cathode, the Anti-Perovskite solid electrolyte is a lithium-Rich Anti-Perovskite solid electrolyte (Li Rich Anti-Perovskite, LiRAP for short).
Preferably, the formula of LiRAP may be Li3-x-δMx/2O(A1-zA′z)1-δWherein 0 is less than or equal toδ≤0.5，0≤x is less than or equal to 2, and z is more than or equal to 0 and less than or equal to 1. M is any one of Ca, Mg, Co, Al and Fe, A and A' independently represent any one of Cl, Br and I. Such as may be Li3-x-δMgx/2O(A1-zA′z)1-δ，Li3-x-δCax/2O(A1-zA′z)1-δWherein 0 is less than or equal toδ≤0.5，0≤x≤2，0≤z≤1，0≤δ≤0.5, 0. ltoreq. x.ltoreq.2, 0. ltoreq. z.ltoreq.1, more particularly Li2.9Mg0.05OCl、Li2.9Ca0.05OCl、Li2.9Fe0.05OCl、Li2.8Mg0.1OCl、Li2.8Ca0.1OCl, and the like.
Still more preferably, Li3-x-δMx/2O(A1-zA′z)1-δIs Li3OCl、Li3OBr、Li3OCl0.5Br0.5Any one of the above.
Whether an electrochemical deposition method or a magnetron sputtering method is adopted, when the prepared cathode is a sodium cathode, the Anti-Perovskite solid electrolyte is a sodium-Rich Anti-Perovskite solid electrolyte (Na Rich Anti-Perovskite is abbreviated as NaRAP).
Preferably, NaRAP may be of the formula Na3-x-δMx/2O(A1-zA′z)1-δWherein 0 is less than or equal toδ≤0.5, x is more than or equal to 0 and less than or equal to 2, and z is more than or equal to 0 and less than or equal to 1. M is any one of Ca, Mg, Co, Al and Fe, A and A' independently represent any one of Cl, Br and I. Such as Na3-x-δMgx/2O(A1-zA′z)1-δ，Na3-x-δCax/2O(A1-zA′z)1-δWherein 0 is less than or equal toδ≤X is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 1, wherein x is more than or equal to 0δ≤3, 0. ltoreq. x.ltoreq.2, 0. ltoreq. z.ltoreq.1, more particularly Na2.9Mg0.05OCl、Na2.9Ca0.05OCl、Na2.9Fe0.05OCl、Na2.8Mg0.1OCl、Na2.8Ca0.1OCl, and the like.
More preferably, Na3-x-δMx/2O(A1-zA′z)1-δIs Na3OBr、Na3Any one of OI.
When the molten anti-perovskite solid electrolyte is coated on the surface of the current collector, a spin coating mode or a blade coating mode can be adopted, and the idea of the invention is that the thickness of the coated anti-perovskite solid electrolyte is controlled to be (1-5) mu m, no matter which mode is adopted for coating. The thickness of the anti-perovskite solid electrolyte membrane formed by the anti-perovskite solid electrolyte with the thickness is (1-5) mu m, so that the effect of an artificial solid electrolyte membrane (SEI) is achieved.
When the electrochemical method is used for depositing lithium or sodium, the electrochemical deposition process is a conventional process, and current parameters and the like can be adjusted according to specific conditions and the thickness of a required lithium metal layer or sodium metal layer. In the electrochemical deposition process, a current collector coated with an anti-perovskite solid electrolyte membrane can be used as a positive electrode, lithium metal or sodium metal can be used as a negative electrode, a battery is assembled, the deposition of the lithium metal or the sodium metal can be realized by constant current discharge, and the discharge current and the discharge time can be determined according to the required negative electrode capacity. And after the electrochemical deposition is finished, disassembling the battery to obtain the lithium cathode or the sodium cathode. In the deposition process, lithium ions or sodium ions pass through the anti-perovskite solid electrolyte membrane and are deposited on the surface of a current collector, and along with the deposition, the anti-perovskite solid electrolyte membrane is propped by a lithium metal layer or a sodium metal layer formed by deposition, separated from the current collector and attached to the surface of the lithium metal layer or the sodium metal layer, so that a lithium negative electrode or a sodium negative electrode with a sandwich structure is finally formed.
Preferably, the current collector of the lithium negative electrode or the sodium negative electrode prepared by the electrochemical method is a copper foil, the copper foil has the characteristics of high melting point, good conductivity, relatively stable chemical properties and the like, the molten anti-perovskite solid electrolyte can be ensured not to be molten when coated on the surface, and due to the good conductivity, the lithium negative electrode or the sodium negative electrode can be well electrochemically deposited, and the lithium negative electrode or the sodium negative electrode can play a good role in conducting and collecting current when assembled into a battery.
When the deposition of the anti-solid electrolyte is realized by adopting a magnetron sputtering mode, the used specific process is a conventional magnetron sputtering process, specifically, the anti-perovskite solid electrolyte can be firstly made into a compact ceramic chip so as to be deposited on the surface of a lithium metal sheet or a sodium metal sheet through magnetron sputtering, and during magnetron sputtering, a layer of anti-perovskite solid electrolyte film is covered on the surface of the lithium metal sheet or the sodium metal sheet.
The anti-perovskite solid electrolyte membrane is formed by magnetron sputtering deposition, and the thickness of the anti-perovskite solid electrolyte membrane is (1-5) mu m, so that the effect of an artificial solid electrolyte membrane (SEI) is achieved.
According to the invention, by an electrochemical method or a magnetron sputtering method, a layer of artificial solid electrolyte membrane is obtained on the surface of the lithium cathode or the sodium cathode, so that the lithium cathode or the sodium cathode has a good and stable SEI membrane structure when assembled into a battery, and the formation of lithium dendrites or sodium dendrites is effectively inhibited, thereby improving the electrochemical performance of the battery.
According to the invention, the lithium cathode or the sodium cathode is obtained through the preparation method of the lithium cathode or the sodium cathode.
The first lithium negative electrode comprises a current collector, a lithium metal layer stacked on the surface of the current collector in a stacked manner and an anti-perovskite solid electrolyte membrane stacked on the surface of the lithium metal layer in a stacked manner; the second lithium negative electrode comprises a lithium metal sheet and an anti-perovskite solid electrolyte membrane coated on the surface of the lithium metal sheet.
The sodium cathode has two structures, wherein the first sodium cathode comprises a current collector, a sodium metal layer stacked on the surface of the current collector in a stacked manner and an anti-perovskite solid electrolyte membrane stacked on the surface of the sodium metal layer in a stacked manner; the second sodium negative electrode comprises a sodium metal sheet and an anti-perovskite solid electrolyte membrane coated on the surface of the sodium metal sheet.
The present invention further provides a lithium battery based on the lithium negative electrode and a sodium battery based on the sodium negative electrode.
The lithium battery is a lithium-sulfur battery and comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and the like, wherein the negative electrode is the lithium negative electrode mentioned in the invention, namely the lithium negative electrode comprises a current collector, a lithium metal layer stacked on the surface of the current collector and an anti-perovskite solid electrolyte membrane stacked on the surface of the lithium metal layer; or the lithium negative electrode comprises a lithium metal sheet and an anti-perovskite solid electrolyte membrane coated on the surface of the lithium metal sheet. The anode can be a sulfur-carbon composite material, and the electrolyte is the electrolyte commonly used for lithium-sulfur batteries.
The sodium battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and the like, wherein the negative electrode is the sodium negative electrode, namely the sodium negative electrode comprises a current collector, a sodium metal layer stacked on the surface of the current collector, and an anti-perovskite solid electrolyte membrane stacked on the surface of the sodium metal layer; or the sodium cathode comprises a sodium metal sheet and an anti-perovskite solid electrolyte membrane coated on the surface of the sodium metal sheet. The positive electrode can be a positive electrode commonly used by sodium batteries, and the electrolyte is an electrolyte commonly used by the sodium batteries.
In order to more effectively explain the technical solution of the present invention, the technical solution of the present invention is explained below by a plurality of specific examples.
Example 1
A method of manufacturing a lithium negative electrode and a lithium-sulfur battery.
The preparation method of the lithium negative electrode comprises the following steps:
s11, in a glove box (control H)2O≤20ppm，O2Less than or equal to 200 ppm) adding 0.2mol of LiOH (purity is more than or equal to 99 percent, produced by alladin) and 0.1mol of LiCl (purity is more than or equal to 99 percent, produced by alladin) into a mortar for grinding and mixing uniformly, then putting into an alumina crucible, heating to 345 +/-15 ℃, keeping vacuum pumping for 24 hours, and obtaining a reaction equation, namely LiCl +2 LiOH-Li3OCl+H2O; the lithium ion conductivity of the obtained lithium ion battery is 10-3～10-5Range of anti-perovskite type solid electrolytes Li3OCl。
To verify that Li was obtained3OCl, XRD test of the material obtained in S11, the results are shown in FIG. 1. As can be seen from FIG. 1, the reaction product obtained is Li3OCl。
S12, the product obtained in the step S11Molten state anti-perovskite solid electrolyte Li3OCl is dripped on the surface of a clean and dry copper foil with the temperature of 340 +/-10 ℃, and a scraper is used for blade coating, so that the molten anti-perovskite solid electrolyte Li3OCl is uniformly coated on the surface of the copper foil, and Li is controlled3OCl thickness of 2 μm, natural cooling to obtain Li with thickness of 2 μm3OCl film to which Li is attached3The copper foil of the OCl film was SEM-scanned, and the results are shown in fig. 2.
As can be seen from FIG. 2, Li3The OCl film is flatly attached to the surface of the copper foil, and still shows extremely high flatness after being amplified. The results of the cross-sectional elemental analysis of the structure shown in FIG. 2 are shown in FIGS. 3, 4 and 5, and it can be seen from FIG. 3 that a layer of Li was formed on the surface of the copper foil3The OCl film, as can be seen from FIGS. 4 and 5, has a distinct double-layer structure, containing Li of chlorine element3OCl is distributed on the upper layer, and copper element is distributed on the upper layer.
S13, adhering Li to the surface obtained in the step S123Cutting the copper foil of the OCl film into a pole piece with the diameter of 16mm, taking the cut pole piece as a positive electrode, taking a lithium metal piece with the diameter of 16mm and the thickness of 0.6mm as a negative electrode, taking the diaphragm as a 2400-type polyethylene diaphragm, and taking an LS-09-type lithium-sulfur electrolyte (the solvent is a mixed solvent of ethylene glycol dimethyl ether (DME) and 1,3 Dioxolane (DOL) in a volume ratio of 1:1, and the solute is 1M LiTFSI, LiNO3The mass concentration is 2 percent), and a 2025 type button cell is assembled; and then placing the obtained 2025 type button cell in a novyi cell charge-discharge testing system, and discharging for 3 hours according to a constant current discharge process with the current of 4mA so as to deposit a lithium metal layer on the surface of the copper foil, thereby obtaining the lithium cathode.
S14, assembling a sulfur-carbon composite positive electrode (carbon fiber is a carrier of the sulfur-carbon composite, the mass ratio of sulfur to carbon is 3:1), a 2400-type polypropylene diaphragm, LS-09 type lithium-sulfur electrolyte and the lithium negative electrode obtained in the step S13 to form the lithium-sulfur battery, wherein the surface density of an active substance of the lithium-sulfur battery is 2.4mg/cm2(ii) a After the detected voltage is normal, the battery is placed in a new power battery charge-discharge tester for charge-discharge test under the test condition of 2mA/cm2The voltage interval is 1.7-2.8V, and the specific result is shown in FIG. 10.
Comparative example 1
A lithium sulfur battery prepared as follows:
D11. cutting the copper foil into pole pieces with the diameter of 16mm, taking the cut pole pieces as positive electrodes, taking lithium metal pieces with the diameter of 16mm and the thickness of 0.6mm as negative electrodes, taking a 2400-type polyethylene diaphragm as a diaphragm, and taking LS-09 type lithium-sulfur electrolyte as electrolyte to assemble a 2025-type button cell; and then placing the obtained 2025 type button cell in a novyi cell charge-discharge testing system, and discharging for 3 hours according to a constant current discharge process with the current of 4mA so as to deposit a lithium metal layer on the surface of the copper foil, thereby obtaining the lithium cathode.
D12. Assembling a sulfur-carbon composite positive electrode (carbon fiber is a carrier of the sulfur-carbon composite, the mass ratio of sulfur to carbon is 3:1), a 2400 type polypropylene diaphragm, LS-09 type lithium sulfur electrolyte and the lithium negative electrode obtained in the step D12 into a lithium-sulfur battery, wherein the surface density of an active substance of the lithium-sulfur battery is 2.38mg/cm2(ii) a After the detected voltage is normal, the battery is placed in a new power battery charge-discharge tester for charge-discharge test under the test condition of 2mA/cm2The voltage interval is 1.7-2.8V, and the test result is shown in FIG. 10.
As can be seen from fig. 10, under the test condition that the charge-discharge rate is 0.5C, the initial specific Capacity of the lithium-sulfur battery of example 1 is 810mAh/g, the specific Capacity (Capacity) of the battery after 250 cycles (Cycle Number) is 630mAh/g, and the Coulombic Efficiency (CE) > 99%; while the initial specific Capacity of the lithium-sulfur battery of comparative example 1 was 800mAh/g, the specific Capacity (Capacity) of the battery after 60 cycles (Cycle Number) was 80mAh/g, and the Coulombic Efficiency (CE) < 95%.
Since the batteries of example 1 and comparative example 1 were prepared in batches, the remaining batteries were analyzed for other properties, such as disassembling the lithium sulfur batteries of example 1 and comparative example 1 respectively subjected to 200 cycles, and 80 cycles, and the lithium negative electrode was cleaned and SEM-scanned, wherein the scanning results of example 1 are shown in fig. 6 and 7, and the scanning results of comparative example 1 are shown in fig. 8 and 9, wherein fig. 6 and 8 are SEM images magnified 2000 times, and fig. 7 and 9 are SEM images magnified 5000 times.
As can be seen from fig. 6 and 7, no lithium dendrite appears on the surface of the lithium negative electrode after 200 cycles.
As can be seen from fig. 8 and 9, a large amount of lithium dendrites appeared on the surface of the lithium negative electrode after 80 cycles.
Example 2
A method of manufacturing a lithium negative electrode and a lithium-sulfur battery.
The preparation method of the lithium negative electrode comprises the following steps:
s21, in a glove box (control H)2O≤20ppm，O2Not more than 200 ppm) 0.2mol of LiOH (purity not less than 99%, produced by aladdin company) and 0.1mol of LiCl (purity not less than 99%, produced by aladdin company) are put into a mortar for grinding and mixing evenly, then put into an alumina crucible for heating to 345 +/-15 ℃ and keeping vacuumizing for 24 hours, and the reaction equation is that LiCl +2LiOH (Li + Li) is expressed by the reaction equation3OCl+H2O; the lithium ion conductivity of the obtained lithium ion battery is 10-3～10-5Range of anti-perovskite type solid electrolytes Li3OCl。
S22, obtaining the anti-perovskite solid electrolyte Li obtained in the step S213Preparing compact ceramic plates from OCl; sputtering the ceramic plate on the surface of a lithium metal plate by adopting a magnetron sputtering deposition mode (sputtering power of 200W, argon pressure of 3m torr, argon flow speed of 3sccn, sputtering time of 20 minutes) to obtain Li with the thickness of 2 mu m3OCl film, thereby obtaining a lithium negative electrode.
S23, assembling a sulfur-carbon composite anode (carbon fiber is a carrier of the sulfur-carbon composite, the mass ratio of sulfur to carbon is 3:1), a 2400-type polypropylene diaphragm, LS-09 type lithium-sulfur electrolyte and the lithium cathode obtained in the step S22 into a lithium-sulfur battery, wherein the surface density of an active substance of the lithium-sulfur battery is 2.4mg/cm2(ii) a After the detected voltage is normal, the battery is placed in a new power battery charge-discharge tester for charge-discharge test under the test condition of 4mA/cm2The voltage interval is 1.7-2.8V, and the specific result is shown in FIG. 11.
Comparative example 2
A lithium sulfur battery prepared as follows:
D21. cutting the copper foil into pole pieces with the diameter of 16mm, taking the cut pole pieces as positive electrodes, taking lithium metal pieces with the diameter of 16mm and the thickness of 0.6mm as negative electrodes, taking a 2400-type polyethylene diaphragm as a diaphragm, and taking LS-09 type lithium-sulfur electrolyte as electrolyte to assemble a 2025-type button cell; and then placing the obtained 2025 type button cell in a novyi cell charge-discharge testing system, and discharging for 3 hours according to a constant current discharge process with the current of 4mA so as to deposit a lithium metal layer on the surface of the copper foil, thereby obtaining the lithium cathode.
D22. Assembling a sulfur-carbon composite positive electrode (carbon fiber is a carrier of the sulfur-carbon composite, the mass ratio of sulfur to carbon is 3:1), a 2400 type polypropylene diaphragm, LS-09 type lithium sulfur electrolyte and the lithium negative electrode obtained in the step D22 into a lithium-sulfur battery, wherein the surface density of an active substance of the lithium-sulfur battery is 2.71mg/cm2(ii) a After the detected voltage is normal, the battery is placed in a new power battery charge-discharge tester for charge-discharge test under the test condition of 4mA/cm2The voltage interval is 1.7-2.8V, and the test result is shown in FIG. 12.
As can be seen from fig. 12, under the test condition of the charge and discharge rate of 0.5C, the initial specific Capacity of the lithium-sulfur battery of example 2 was 700mAh/g, the specific Capacity (Capacity) of the battery was 550mAh/g and the Coulombic Efficiency (CE) was > 99% through 500 cycles (Cycle Number), while the initial specific Capacity of the lithium-sulfur battery of comparative example 2 was 710mAh/g, the specific Capacity (Capacity) of the battery was 100mAh/g through 60 cycles (Cycle Number), and the Coulombic Efficiency (CE) was < 93%.
Example 3
A preparation method of a sodium cathode and a sodium battery are provided. The preparation method of the sodium cathode comprises the following steps:
s31, in a glove box (control H)2O≤20ppm，O2Less than or equal to 200 ppm) is added with 0.1mol of Na2O (the purity is more than or equal to 95 percent) and 0.1mol of NaBr (the purity is more than or equal to 99 percent) are put into an alumina crucible to be ground and mixed evenly, then the mixture and the alumina crucible are put into a tube furnace to be heated to 400 ℃ and kept vacuumized for 4 hours, and the reaction equation is Na2O+NaBr＝Na3OBr; the conductivity of sodium ion is 10-4-10-7Range of anti-perovskite type solid electrolytes Na3OBr。
S32, melting state obtained in step S31Is a perovskite-resistant solid electrolyte Na3Dripping OBr on the surface of clean and dry copper foil with the temperature of (400 +/-10) DEG C, and scraping by a scraper to ensure that the molten anti-perovskite solid electrolyte Na3OBr is uniformly coated on the surface of copper foil, and Na is controlled3The thickness of OBr was 2 μm, and the obtained product was naturally cooled to obtain Na having a thickness of 2 μm3An OBr film.
S33, adhering Na to the surface obtained in the step S323Cutting a copper foil of the OBr film into pole pieces with the diameter of 16mm, taking the cut pole pieces as a positive electrode, taking a sodium metal piece with the diameter of 16mm and the thickness of 0.6mm as a negative electrode, taking the diaphragm as a 2400-type polyethylene diaphragm, and assembling the electrolyte into a 2025-type button cell by using NS-08 type sodium-sulfur electrolyte (the solvent is a mixed solvent of ethylene glycol dimethyl ether (DME) and 1,3 Dioxolane (DOL), the volume ratio of the two is 1:1, and the solute is 1M NaTFSI); and then placing the obtained 2025 type button cell in a novyi cell charge-discharge testing system, and discharging for 3 hours according to a constant current discharge process with the current of 4mA so as to deposit a sodium metal layer on the surface of the copper foil, thereby obtaining the sodium cathode.
S34, assembling a sulfur-carbon composite anode (carbon fiber is a carrier of the sulfur-carbon composite, the mass ratio of sulfur to carbon is 3:1), a 2400-type polypropylene diaphragm, an NS-08 type sodium-sulfur electrolyte and the sodium cathode obtained in the step S33 to form the sodium-sulfur battery, wherein the surface density of an active substance sulfur of the sodium-sulfur battery is 5.1mg/cm2After the detected voltage is normal, the battery is placed in a new power battery charge-discharge tester for charge-discharge test. At a current density of 2mA/cm2Under the test conditions of (1), the initial specific Capacity is 605mAh/g, the specific Capacity (Capacity) of the battery after 80 cycles is 550mAh/g, and the Coulombic Efficiency (CE)>95％.。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method of making a lithium or sodium anode, comprising the steps of:
providing an anti-perovskite solid electrolyte, melting the anti-perovskite solid electrolyte, and coating the melted anti-perovskite solid electrolyte on the surface of a current collector so as to form a layer of anti-perovskite solid electrolyte film on the surface of the current collector;
depositing lithium or sodium on the surface of the current collector by adopting an electrochemical method to obtain a lithium cathode or a sodium cathode;
alternatively, the first and second electrodes may be,
and depositing the anti-perovskite solid electrolyte on the surface of a lithium metal sheet or a sodium metal sheet in a magnetron sputtering mode, so as to form a layer of anti-perovskite solid electrolyte membrane on the surface of the lithium metal sheet or the sodium metal sheet, and thus obtaining the lithium cathode or the sodium cathode.
2. The method for producing a lithium or sodium negative electrode according to claim 1, wherein the thickness of the formed anti-perovskite solid electrolyte membrane is (1 to 5) μm.
3. The method for producing a lithium negative electrode or a sodium negative electrode according to claim 1, wherein when a lithium negative electrode is produced, the anti-perovskite solid electrolyte is LiRAP; when a sodium negative electrode is prepared, the anti-perovskite solid electrolyte is NaRAP.
4. The method of preparing a lithium or sodium anode of claim 3, wherein the LiRAP is Li3OCl、Li3OBr、Li3OCl0.5Br0.5Any one of (a);
the NaRAP is Na3OBr、Na3Any one of OI.
5. The lithium negative electrode or the sodium negative electrode is characterized by comprising a current collector, a lithium metal layer stacked on the surface of the current collector, and an anti-perovskite solid electrolyte membrane stacked on the surface of the lithium metal layer; or the lithium negative electrode comprises a lithium metal sheet and an anti-perovskite solid electrolyte membrane coated on the surface of the lithium metal sheet;
the sodium negative electrode comprises a current collector, a sodium metal layer stacked on the surface of the current collector, and an anti-perovskite solid electrolyte membrane stacked on the surface of the sodium metal layer; or the sodium negative electrode comprises a sodium metal sheet and an anti-perovskite solid electrolyte membrane coated on the surface of the sodium metal sheet.
6. The lithium or sodium negative electrode according to claim 5, wherein the thickness of the anti-perovskite solid electrolyte membrane is (1 to 5) μm.
7. The lithium or sodium anode of claim 5, wherein, when a lithium anode, the material of the anti-perovskite solid electrolyte membrane is LiRAP; when the material is a sodium negative electrode, the material of the anti-perovskite solid electrolyte membrane is NaRAP.
8. The lithium or sodium anode of claim 7, wherein the LiRAP is Li3OCl、Li3OBr、Li3OCl0.5Br0.5Any one of (a);
the NaRAP is Na3OBr、Na3Any one of OI.
9. A lithium battery, which is a lithium-sulfur battery and comprises a lithium negative electrode, wherein the lithium negative electrode is the lithium negative electrode prepared by the preparation method of any one of claims 1 to 4 or the lithium negative electrode of any one of claims 5 to 8.
10. A sodium battery comprises a sodium negative electrode, and is characterized in that the sodium negative electrode is prepared by the preparation method of any one of claims 1 to 4 or the sodium negative electrode of any one of claims 5 to 8.
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