CN117253966B - Method for constructing stable interface film on alkali metal surface by utilizing neutron irradiation - Google Patents

Method for constructing stable interface film on alkali metal surface by utilizing neutron irradiation Download PDF

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CN117253966B
CN117253966B CN202311250923.8A CN202311250923A CN117253966B CN 117253966 B CN117253966 B CN 117253966B CN 202311250923 A CN202311250923 A CN 202311250923A CN 117253966 B CN117253966 B CN 117253966B
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alkali metal
irradiation
film
neutron irradiation
lithium
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CN117253966A (en
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方姗
周耐根
刘翔
饶玉鑫
李雪
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Nanchang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention belongs to the technical field of alkali metal secondary batteries of chemical power supplies, and relates to a method for constructing a stable interface film on the surface of alkali metal by utilizing neutron irradiation. By using different salts and solvents as irradiation media, neutron irradiation treatment is adopted to excite the irradiation media to generate free radicals, electrons, ions and the like to react with an alkali metal negative electrode, so that the SEI film with good ion conductivity and mechanical strength is obtained. By changing the components, concentration and irradiation dose of the irradiation medium, SEI films rich in inorganic components with different properties are obtained, and the circulation stability of the alkali metal cathode in the alkali metal battery is improved.

Description

Method for constructing stable interface film on alkali metal surface by utilizing neutron irradiation
Technical Field
The invention belongs to the technical field of alkali metal secondary batteries of chemical power supplies, and particularly relates to a method for constructing a stable interfacial film on the surface of alkali metal by utilizing neutron irradiation.
Background
The lithium metal negative electrode becomes a 'holy cup' of the battery energy storage world with its theoretical capacity (3860 mAh.g -1, graphite negative electrode: 372 mAh.g -1) ten times that of a traditional graphite negative electrode and the most negative potential (-3.045V, relative to a standard hydrogen electrode). When the lithium metal negative electrode is matched with the high-energy-density high-nickel ternary positive electrode, the energy density of the battery is expected to be further improved. The main problem of limiting the application of lithium metal cathode at present is that lithium ions are unevenly deposited on the surface of the cathode in the charge and discharge process, so that dendrite growth is caused, the stability of solid electrolyte interface film SEI is further destroyed, and meanwhile, more side reactions are caused by dendrite growth, so that the coulomb efficiency is reduced. In addition, the lithium negative electrode is subjected to pulverization due to infinite volume expansion, the cycling stability is poor, the electrode is finally disabled, potential safety hazards are caused when the electrode is more serious, and the practical application of the lithium metal negative electrode is hindered.
One of the important methods for improving the interfacial stability of lithium metal negative electrodes is to form a layer of Solid Electrolyte (SEI) film on the surface of the lithium metal negative electrode, and the protective layer has higher lithium ion conductivity and certain flexibility, so that the growth of dendrites can be well inhibited. The inorganic-organic polymer composite artificial SEI film has good flexibility, good flexibility and ion conductivity, and can effectively relieve dendrite growth. However, the polymer swells in the liquid electrolyte, which affects ion transport in the SEI layer, thereby affecting long-cycle performance of the battery. The SEI film rich in inorganic components has higher ionic conductivity, and can be obtained by atomic layer deposition or magnetron sputtering, or by adopting inorganic salts such as CuCl 2、SbF3 and the like which can react with lithium metal chemically, but the method has certain limitations, the coating layer can bring new interface compatibility problem, and the intrinsic water oxygen sensitivity of the lithium metal is not beneficial to practical production and application. The stable interface layer is obtained by electrolyte additives or electrolyte formulation regulation, but effective lithium salts and electrolyte components are limited, and electrolyte regulation needs to consider various physical and chemical parameters of various salts and solvents, solvation structures and the like, and can be influenced by formation conditions such as voltage, current, temperature and the like.
Therefore, it is necessary to develop a high-efficiency and convenient method for constructing an alkali metal interface film, and constructing a high-efficiency and stable SEI film on the surface of the alkali metal is important for realizing the practical application of the lithium metal battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for constructing a stable interface film on the surface of alkali metal by utilizing neutron irradiation. By using different salts and solvents as irradiation media and adopting neutron irradiation treatment to excite the irradiation media to generate free radicals, electrons, ions and the like to react with the alkali metal cathode, the SEI film with good ion conductivity and mechanical strength is obtained. By changing the components, concentration and irradiation dose of the irradiation medium, SEI films rich in inorganic components with different chemical compositions and structures are obtained, and the circulation stability of the alkali metal cathode in the alkali metal battery is improved.
In order to achieve the above purpose, the present invention provides the following technical solutions:
One of the technical schemes of the invention is as follows: a method for constructing a stable interfacial film on an alkali metal surface using neutron irradiation is provided, comprising the steps of:
and (3) treating alkali metal immersed in an irradiation medium by neutron irradiation, wherein a solid electrolyte interface film generated in situ on the surface of the alkali metal is the stable interface film.
Further, the irradiation dose of the neutron irradiation treatment is 10Gry-1000Gry.
Further, the irradiation medium is a solution composed of salt and solvent and having a concentration of 1-4 mol/L.
Preferably, the salt includes one of lithium hexafluorophosphate (LiPF 6), lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonate) imide (LiTFSI), sodium hexafluorophosphate (NaPF 6), sodium bis (fluorosulfonyl) imide (NaFSI), and sodium bis (trifluoromethanesulfonyl) imide (NaTFSI).
Preferably, the solvent includes one or two of dimethyl carbonate (DMC), ethylene Carbonate (EC), vinylene Carbonate (VC), fluoroethylene carbonate (FEC) and diethyl carbonate (DEC).
Further, the alkali metal is lithium metal or sodium metal.
The second technical scheme of the invention is as follows: an alkali metal having a stable interfacial film prepared by the above method is provided.
The third technical scheme of the invention: use of an alkali metal having a stable interfacial film as described above in assembling an alkali metal cell.
Further, the application in the assembled alkali metal cell is specifically as follows: an alkali metal having a stable interfacial film is used as a negative electrode of an alkali metal cell.
Compared with the prior art, the technical scheme has the following beneficial effects:
The method adopts a physical and chemical combination method, and a large amount of excited states, electrons and free radicals can be generated in a solution system through neutron irradiation, and the excited states are rapidly converted into free radicals and neutral molecules with rich types, so that the radiation chemical reaction involving the intermediate states of the free radicals is driven. On the other hand, due to the intrinsic reaction characteristics, elements such as lithium, boron, nitrogen, sulfur and phosphorus have larger absorption cross sections for neutrons, are extremely easy to react with neutrons, and are very compatible with elements related to lithium salts of a lithium secondary battery system. Thus, it is easier to promote radiochemical reactions that are based on lithium salts exciting the ionization products. The salt and the solvent which are beneficial to the alkali metal can be optimized, and the interfacial film can be efficiently and rapidly formed without considering complex physical parameters, solvation structures and formation conditions, so that the interfacial stability of the alkali metal cathode is improved, and the electrochemical performance of the alkali metal battery is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
fig. 1 is an XPS comparison graph of lithium metal anodes of example 1 and comparative example 1.
FIG. 2 is a graph of the cycle performance of the symmetric cell prepared in example 1 at a current density of 1mA/cm 2 and a deposition capacity of 1mAh/cm 2, wherein the left graph shows a long cycle life and the right graph shows a time-voltage curve with partial amplification for 800-810 h.
FIG. 3 is a graph showing the cycle performance of the symmetric battery prepared in example 1 under the conditions of a current density of 2mA/cm 2 and a deposition capacity of 1mAh/cm 2, wherein the left graph shows a long cycle life graph and the right graph shows a time-voltage curve locally enlarged for 250-260 h.
FIG. 4 is a graph of the cycle performance of the symmetric cell prepared in example 2 at a current density of 1mA/cm 2 and a deposition capacity of 1mAh/cm 2, wherein the left graph is a long cycle life graph and the right graph is a time-voltage curve with partial amplification for 800-810 h.
FIG. 5 is a graph showing the cycle performance of the symmetrical cells prepared in comparative examples 1 and 2 at a current density of 1mA/cm 2 and a deposition capacity of 1mAh/cm 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of symmetrical cell:
s1, preparing a solution with concentration of 1mol/L as an irradiation medium by taking LiFSI as lithium salt and FEC as a solvent.
S2, adding the lithium sheet into an irradiation medium, completely soaking, and sealing to obtain a sealed sample.
S3, placing the sealed sample into an irradiation center for neutron irradiation, wherein the irradiation dose is 10Gry, and obtaining an irradiation sample.
And S4, taking out the irradiation sample, flushing the surface by DMC, and drying to obtain the lithium metal (alkali metal) anode with the stable interface film.
S5, a lithium metal (alkali metal) negative electrode assembly button CR2032 symmetrical battery with a stable interface film is adopted, wherein electrolyte is 1M LiPF 6, EC/DEC (1:1, v/v), 10wt% of FEC is adopted, and the electrolyte dosage is 40 mu L.
The assembled button CR2032 symmetrical battery is subjected to a cyclic test under the conditions of a current density of 1mA/cm 2 and a deposition capacity of 1mAh/cm 2, and can be stably circulated for 1100h, and the polarization voltage is 94mV.
The cyclic test is carried out under the condition that the current density is 2mA/cm 2 and the deposition capacity is 1mAh/cm 2, and the cyclic test can be stably carried out for 300h, and the polarization voltage is 113mV.
Example 2
The only difference compared to example 1 is that the lithium salt LiFeSI is replaced by LiTFSI.
The assembled button CR2032 symmetrical battery is subjected to cycle test under the conditions of current density of 1mA/cm 2 and deposition capacity of 1mAh/cm 2, and can be stably cycled for 900 hours, and the polarization voltage is 94mV.
The cyclic test was carried out at a current density of 2mA/cm 2 and a deposition capacity of 1mAh/cm 2, and the cyclic test was carried out for 300 hours with a polarization voltage of 246mV.
Example 3
The only difference compared to example 1 is that the irradiation dose is 0Gry, 20Gry, 50Gry or 100Gry.
The assembled button CR2032 symmetric battery was subjected to a cycle test at a current density of 1mA/cm 2 and a deposition capacity of 1mAh/cm 2, and the cycle performance is shown in Table 1 below.
TABLE 1
As can be seen from table 1, as the irradiation dose increases, the polarization is severe and the cycle life is shortened, mainly because the irradiation medium and the alkali metal itself are destroyed under the irradiation of a large dose, and therefore, an appropriate irradiation dose needs to be selected for different irradiation media and alkali metals.
Comparative example 1
The difference compared with example 1 is only that the lithium sheet was subjected to a stand-alone treatment after being added to the irradiation medium to obtain a lithium metal (alkali metal) anode.
Comparative example 2
The difference compared with example 2 is only that the lithium sheet was subjected to a stand-alone treatment after being added to the irradiation medium to obtain a lithium metal (alkali metal) anode.
Fig. 1 is an XPS comparison graph of lithium metal anodes of example 1 and comparative example 1. From fig. 1, it can be seen that the surface SEI composition of irradiated lithium metal (example 1) and non-irradiated lithium metal (comparative example 1) is substantially the same, and Li 2CO3 is newly added in the irradiated lithium metal surface SEI film. However, the component contents of SEI are obviously different, and as can be seen from comparison of S2p and F1S in FIG. 1, the fact that the irradiated lithium metal surface has higher-SoxF and-Sox, liF, S-F bond content indicates that the irradiation medium is seriously decomposed, and the surface cannot generate a compact and uniform SEI layer. In contrast, since a stable SEI layer is generated on the surface of lithium metal after neutron irradiation, the irradiation medium is prevented from further reacting with lithium metal.
FIG. 2 is a graph of ring performance of the symmetric cell prepared in example 1 with a current density of 1mA/cm 2 and a deposition capacity of 1mAh/cm 2, wherein the left graph shows a long cycle life and the right graph shows a time-voltage curve with partial amplification for 800-810 h. It can be seen from fig. 2 that the cycle life of the symmetrical cell after irradiation treatment is nearly doubled, and the polarization voltage is small, which is maintained at 90mV.
FIG. 3 is a graph showing the cycle performance of the symmetric battery prepared in example 1 under the conditions of a current density of 2mA/cm 2 and a deposition capacity of 1mAh/cm 2, wherein the left graph shows a long cycle life graph and the right graph shows a time-voltage curve locally enlarged for 250-260 h. As can be seen from FIG. 3, the cycle was stable for 300 hours even at a relatively large current density of 2mA/cm 2, and the polarization voltage was 113mV.
FIG. 4 is a graph of the cycle performance of the symmetric cell prepared in example 2 at a current density of 1mA/cm 2 and a deposition capacity of 1mAh/cm 2, wherein the left graph is a long cycle life graph and the right graph is a time-voltage curve with partial amplification for 800-810 h. From FIG. 4, it can be seen that the irradiation medium with LiTFSI as lithium salt can be stably circulated for 900 hours under the condition of 1mA/cm 2, the polarization voltage is 94mV, and the electrochemical performance is superior to that of the non-irradiated lithium metal (comparative example 2).
FIG. 5 shows the cycling performance of the symmetrical cells prepared in comparative examples 1 and 2 at a current density of 1mA/cm 2 and a deposition capacity of 1mAh/cm 2. It can be seen from FIG. 5 that the unirradiated lithium metal anode has poor cycling stability, and the polarization voltage increases significantly after 600 hours of cycling under the cycling condition of 1mA/cm 2,1mAh/cm2, and the voltage increases suddenly from 100mV to 180mV.
The electrochemical performance of the lithium deposition/stripping electrode is obviously reduced compared with that of the non-irradiated lithium metal battery (comparative example 1 and comparative example 2) in examples 1-2, and the cycle life and the cycle stability are obviously improved.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (4)

1. A method for constructing a stable interfacial film on an alkali metal surface using neutron irradiation, comprising the steps of:
preparing a salt and a solvent as an irradiation medium;
Immersing alkali metal in the irradiation medium, and then adopting neutron irradiation treatment to obtain a solid electrolyte interface film generated on the surface of the alkali metal in situ, thereby obtaining the alkali metal with a stable interface film;
The irradiation dose of the neutron irradiation treatment is 10Gry-1000Gry;
The concentration of the irradiation medium is 1-4 mol/L;
The salt comprises one of LiPF 6、LiFSI、LiTFSI、NaPF6, naFSI, and NaTFSI;
the solvent comprises one or both of DMC, EC, VC, FEC and DEC;
the alkali metal is lithium metal or sodium metal.
2. An alkali metal having a stable interfacial film produced by the process of claim 1.
3. Use of an alkali metal with a stable interfacial film according to claim 2 in assembling an alkali metal cell.
4. Use according to claim 3, characterized in that an alkali metal with a stable interfacial film is used as the negative electrode of an alkali metal cell.
CN202311250923.8A 2023-09-26 2023-09-26 Method for constructing stable interface film on alkali metal surface by utilizing neutron irradiation Active CN117253966B (en)

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US7455722B2 (en) * 2005-07-26 2008-11-25 Honda Motor Co., Ltd Ion irradiated electrolyte membrane, anode, and/or cathode
CN112285137A (en) * 2020-10-16 2021-01-29 合肥国轩高科动力能源有限公司 Lithium ion battery full life cycle lithium analysis distribution detection method
US20230251236A1 (en) * 2022-02-09 2023-08-10 The Regents Of The University Of California Titration-gas chromatography method and system for anode detection and quantification in energy storage devices
CN114975897A (en) * 2022-04-08 2022-08-30 苏州纳谷新材料科技有限公司 Alkali metal cathode with stable circulation, preparation method thereof and alkali metal battery

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