CN115928011A - Sodium metal negative electrode protection method and battery - Google Patents
Sodium metal negative electrode protection method and battery Download PDFInfo
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000011241 protective layer Substances 0.000 claims abstract description 48
- 238000000151 deposition Methods 0.000 claims abstract description 42
- 230000008021 deposition Effects 0.000 claims abstract description 39
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 31
- 239000011734 sodium Substances 0.000 claims abstract description 31
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 25
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000019983 sodium metaphosphate Nutrition 0.000 claims abstract description 20
- 239000013077 target material Substances 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 14
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 14
- 239000002344 surface layer Substances 0.000 claims abstract description 11
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 6
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 5
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 5
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 5
- 235000019830 sodium polyphosphate Nutrition 0.000 claims abstract description 4
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 4
- 235000015424 sodium Nutrition 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 18
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001771 vacuum deposition Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 10
- 229920000137 polyphosphoric acid Polymers 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
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- 230000002829 reductive effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021312 NaFePO4 Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the technical field of energy storage batteries, in particular to a sodium metal negative electrode protection method and a battery, wherein the protection method comprises the following steps: the method comprises the steps of taking a sodium sheet as a substrate, taking a protective layer as a target material, controlling the deposition thickness of a protective layer of a metal sodium surface layer by adjusting the deposition time by utilizing a vacuum magnetron sputtering process, wherein the deposition thickness of the protective layer is 100-500nm, depositing the protective layer on the sodium metal surface layer to realize the protection of a sodium metal cathode, and the protective layer is inorganic sodium salt containing a P-O bond. The protective layer is selected from any one of sodium metaphosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium hexapolyphosphate, sodium polyphosphate and sodium phosphate. The protection method can inhibit the contact between the electrolyte and the sodium metal, greatly improve the stability of the sodium metal interface, and minimize the interface impedance caused by the addition of the protective layer.
Description
Technical Field
The invention relates to a sodium metal negative electrode protection method and a battery, and belongs to the technical field of energy storage batteries.
Background
In the working process of the battery, dendritic crystals are generated on the surface of the lithium metal cathode in the charging and discharging processes, and the growth of the lithium dendritic crystals threatens the safe use of the lithium metal battery. Similarly, when sodium metal is used as the negative electrode, sodium dendrite formation during cycling can lead to the continued formation and rupture of the solid electrolyte interfacial film, further consuming sodium metal and electrolyte, due to the higher activity of sodium. During continuous circulation, effective sodium ion migration is hindered by accumulation of 'dead sodium' and a solid electrolyte interface film, polarization of the battery is increased, coulombic efficiency is low, circulation stability is poor, certain potential safety hazards exist, and practical application of the sodium metal battery is hindered.
Based on the above discussion, reducing side reactions of sodium metal with the electrolyte, inhibiting the growth of sodium dendrites, solving interfacial peeling and protective layer breakage caused during expansion-contraction are essential conditions for realizing commercial application of sodium metal negative electrodes.
At present, the prior art processes for solving these problems mainly focus on the optimization of the electrolyte, the modification of the solid electrolyte film (SEI film), the improvement of the separator, and the like. Although the processes can reduce side reactions, some organic solvents used in the processes, such as epoxy resin, naphthalene, naphthol, polyacrylic acid, polyphosphoric acid and the like, can directly react with sodium metal to generate bubbles, polyethylene oxide, polyionic liquid and the like cannot directly infiltrate with sodium metal, and the bubbles can cause poor film forming quality or nonuniform thickness of a protective layer, further increase the internal impedance of the battery and further influence the cycle stability of the battery.
In addition, a negative electrode protection material and a negative electrode sheet for a lithium metal battery and a preparation method thereof are disclosed in the patent publication CN110993945A, and a sodium metal negative electrode protection layer, a sodium metal negative electrode and a preparation method and application thereof are disclosed in the patent publication CN 112531145A.
Disclosure of Invention
The invention provides a sodium metal cathode protection method and a battery, aiming at the problems that in the charge-discharge cycle process of the cathode of the existing metal sodium secondary battery, due to the high activity of the cathode of the sodium metal, the interface of the sodium metal is unstable, and further the cycle performance is poor, the coulombic efficiency is low, the safety is poor and the like, wherein the protection method can inhibit the contact between electrolyte and the sodium metal, so that the stability of the interface of the sodium metal is greatly improved, and the interface impedance caused by the addition of a protection layer can be minimized.
The technical scheme for solving the technical problems is as follows: a protection method of a sodium metal negative electrode comprises the following steps: the sodium sheet is used as a substrate, the protective layer is used as a target material, the protective layer is deposited on the surface layer of the sodium metal by utilizing a vacuum magnetron sputtering process, the protection of the sodium metal cathode is realized, and the protective layer is inorganic sodium salt containing a P-O bond.
Further, the protective layer is selected from any one of sodium metaphosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium hexapolyphosphate, sodium polyphosphate and sodium phosphate.
Preferably, the protective layer is sodium metaphosphate.
Further, the deposition thickness of the metal sodium surface layer protection layer is controlled by adjusting the deposition time by utilizing a vacuum magnetron sputtering process, and the deposition thickness of the protection layer is 100-500nm.
Preferably, the protective layer is sodium metaphosphate, and the deposition thickness of the sodium metaphosphate is 200nm.
Preferably, the protective layer is sodium tripolyphosphate, and the deposition thickness of the sodium tripolyphosphate is 100nm.
Further, the vacuum magnetron sputtering process conditions are as follows: the pressure was-0.1 Kpa and the deposition rate was 100nm/h under an argon atmosphere.
The invention also discloses a battery which comprises a negative electrode, a positive electrode, electrolyte and a diaphragm, wherein the negative electrode is the sodium metal negative electrode protected by the protection method.
Furthermore, the battery is a CR2032 button battery.
Further, the mass ratio of each component in the positive electrode is NaFePO4: SP: PVDF = 96; the electrolyte is 1mol/L NaPF6 dissolved in DME, and the diaphragm is a glass fiber diaphragm.
The beneficial effects of the invention are:
1) The protection method of the sodium metal cathode provided by the invention deposits a protective layer on the surface layer of the sodium metal by a vacuum magnetron sputtering process. The process effectively avoids direct contact between electrolyte and sodium metal by means of excellent chemical stability of the protective layer, so that the stability of a sodium metal interface is greatly improved, and the electrochemical performance of the battery is improved.
2) According to the method for protecting the sodium metal cathode, the deposition thickness of the sodium metal layer protection layer is controlled through a vacuum magnetron sputtering process, and the inorganic sodium salt containing a P-O bond is used as the protection layer of the sodium metal electrode, so that direct contact between electrolyte and sodium metal can be inhibited, and interface impedance caused by adding the protection layer can be minimized.
3) According to the invention, the protective layer is deposited on the surface layer of the sodium metal, and the deposition thickness of the protective layer is adjusted, so that the contact and reaction between the electrolyte and the sodium metal are effectively reduced, the interface stability of the sodium metal is improved, and the defect that the internal resistance of the battery is greatly increased due to the uneven thickness in the conventional protective layer adding process is avoided.
4) The method for protecting the sodium metal cathode has the advantages of simple process, controllable operation process and huge application prospect.
Drawings
FIG. 1 is a graph of 100 cycles of the cells of example 2 and comparative examples 1 and 2 at 0.5C at 2.0-4.0V.
Detailed Description
The following is a detailed description of specific embodiments of the invention. The present invention may be embodied in many different forms than those specifically described herein and those skilled in the art will be able to make similar modifications without departing from the spirit of the invention and it is therefore not intended to be limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
A method of protecting a sodium metal anode comprising the steps of:
1) Pressing the protective layer material into a target material;
2) Vacuumizing under argon atmosphere, wherein the pressure is-0.1 KPa;
3) Performing vacuum magnetron sputtering, depositing a protective layer on the sodium metal surface layer by using a vacuum magnetron sputtering process, and controlling the deposition thickness of the metal sodium surface layer protective layer by adjusting the deposition time, wherein the deposition thickness of the protective layer is 100-500nm;
4) After inflation, the samples were taken out, the cells were assembled, and the tests were performed.
The operations involved in assembling the cell and testing are as follows:
(1) The electrolyte is 1mol/L NaPF 6 The solvent is DME (ethylene glycol dimethyl ether);
(2) The diaphragm is a glass fiber diaphragm, and the thickness of the diaphragm is 100 mu m;
(3) The anode is NaFePO 4 ；
(4) The mass ratio of each component of the positive plate is NaFePO 4 :SP:PVDF=96:2:2；
(5) The surface density of the positive electrode is 10mg/cm 2 ；
(6) The current density was 0.5C.
The preparation process of the sodium metal negative electrode protection method provided by the invention is further described in detail by specific examples.
Example 1
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium metaphosphate as a target material, carrying out vacuum deposition on a sodium sheet for 1h (deposition rate of 1h = 100nm) to obtain a protected sodium metal cathode, then assembling the battery, and testing the interface impedance and the cycle performance.
Example 2
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium metaphosphate as a target material, carrying out vacuum deposition on a sodium sheet for 2 hours (deposition rate is 1h = 100nm) to obtain a protected sodium metal cathode, then assembling the battery, and testing the interface impedance and the cycle performance.
Example 3
And (3) performing vacuum deposition on a sodium sheet for 3 hours (deposition rate is 1h = 100nm) by using sodium metaphosphate as a target under the pressure of-0.1 KPa in the argon atmosphere to obtain a protected sodium metal cathode, assembling the battery, and testing the interface impedance and the cycle performance.
Example 4
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium metaphosphate as a target material, carrying out vacuum deposition on a sodium sheet for 4 hours (deposition rate is 1h = 100nm) to obtain a protected sodium metal cathode, then assembling the battery, and testing the interface impedance and the cycle performance.
Example 5
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium metaphosphate as a target material, carrying out vacuum deposition on a sodium sheet for 5 hours (deposition rate is 1h = 100nm) to obtain a protected sodium metal cathode, then assembling the battery, and testing the interface impedance and the cycle performance.
Example 6
Under the argon atmosphere and the pressure of-0.1 KPa, sodium tripolyphosphate (Zhengzhou alpha chemical Co., ltd.) is taken as a target material, after vacuum deposition is carried out on a sodium sheet for 1h (deposition rate is 1h = 100nm), a protected sodium metal cathode is obtained, then a battery is assembled, and the interface impedance and the cycle performance are tested.
Example 7
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium tripolyphosphate as a target material, carrying out vacuum deposition on a sodium sheet for 2 hours (deposition rate is 1h = 100nm) to obtain a protected sodium metal cathode, then assembling the battery, and testing the interface impedance and the cycle performance.
Example 8
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium tripolyphosphate as a target material, carrying out vacuum deposition on a sodium sheet for 3h (deposition rate is 1h = 100nm) to obtain a protected sodium metal cathode, then assembling the battery, and testing the interface impedance and the cycle performance.
Example 9
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium tripolyphosphate as a target material, carrying out vacuum deposition on a sodium sheet for 4 hours (deposition rate is 1h = 100nm) to obtain a protected sodium metal cathode, then assembling the battery, and testing the interface impedance and the cycle performance.
Example 10
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium tripolyphosphate as a target material, carrying out vacuum deposition on a sodium sheet for 5 hours (deposition rate is 1h = 100nm) to obtain a protected sodium metal negative electrode, then assembling the battery, and testing the interface impedance and the cycle performance.
Example 11
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium phosphate as a target material, carrying out vacuum deposition on a sodium sheet for 2 hours (deposition rate is 1h = 100nm) to obtain a protected sodium metal cathode, then assembling the battery, and testing the interface impedance and the cycle performance.
Example 12
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium pyrophosphate as a target material, carrying out vacuum deposition on a sodium sheet for 2 hours (deposition rate of 1h = 100nm) to obtain a protected sodium metal cathode, then assembling the battery, and testing the interface impedance and the cycle performance.
Comparative example 1
The cell was assembled directly using untreated sodium metal and the interfacial resistance and cycling performance were tested.
Comparative example 2
Weighing 5 parts of PVDF, dissolving in 100 parts of NMP, taking 95 parts of sodium metaphosphate, uniformly dispersing, coating a protective layer on the surface of the sodium metal in a spin coating mode, drying, measuring the thickness of the protective layer to be about 500nm, assembling the battery, and testing the interface impedance and the cycle performance.
Comparative example 3
In the argon atmosphere, polyphosphoric acid (Merck Sigma-Aldrich) is taken as a target material under the pressure of-0.1 KPa, a sodium sheet is subjected to vacuum deposition for 2 hours (deposition rate is 1h = 100nm), a protected sodium metal negative electrode is obtained, and then a battery is assembled to test the interface impedance and the cycle performance.
Comparative example 4
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium metaphosphate as a target material, carrying out vacuum deposition on a sodium sheet for 0.5h (deposition rate is 1h = 100nm) to obtain a protected sodium metal cathode, then assembling the battery, and testing the interface impedance and the cycle performance.
Comparative example 5
And (3) in an argon atmosphere, under the pressure of-0.1 KPa, taking sodium metaphosphate as a target material, carrying out vacuum deposition on a sodium sheet for 6 hours (deposition rate is 1h = 100nm) to obtain a protected sodium metal cathode, then assembling the battery, and testing the interface impedance and the cycle performance.
The interfacial resistance and cycling performance data for examples 1-12 and comparative examples 1-5 are shown in table 1, and the cells of example 2 and comparative examples 1 and 2 are shown in fig. 1 for 100 cycles at 2.0-4.0V at 0.5C.
Table 1 shows the interfacial resistance and capacity retention ratios of examples 1 to 12 and comparative examples 1 to 5
In combination with table 1, it can be found that:
1) As can be seen by comparing the data of examples 1-12: the interface impedance is influenced by the deposition thickness, namely the thicker the deposition thickness is, the larger the interface impedance is, but the deposition thickness needs to reach a certain thickness, so that the contact between the electrolyte and the sodium metal can be effectively avoided, namely, the stability of the interface is kept in the subsequent circulation.
2) Comparing the data of examples 1-5 and comparative examples 4-5, it can be seen that: when the thickness of the protective layer is smaller (comparative example 4), the cycling stability of the battery is poor, and the sodium metal electrode cannot be well protected due to the fact that the thickness of the protective layer is too small; in addition, when the thickness of the protective layer is thick (comparative example 5), the interfacial resistance is increased, which affects the application properties of the battery. Therefore, the thickness of the protective layer is beneficial to better protecting the sodium metal electrode, and the electrode is prevented from having higher impedance.
Meanwhile, the optimal deposition thickness of the sodium metaphosphate on the metal sodium layer is 200nm, and the optimal deposition thickness of the sodium tripolyphosphate on the metal sodium layer is 100nm.
3) Comparing the data of examples 1-12 and comparative example 1, it can be seen that the addition of the protective layer sodium metaphosphate has a significant promoting effect on the modification of the sodium metal interface, i.e., the interfacial impedance in the cyclic process can be effectively reduced, and a better cyclic effect than that without modification can be achieved.
4) Comparing the data of examples 1-12 with comparative example 2, it can be seen that: compared with the conventional sodium metal protective layer preparation process (coating mode), the vacuum magnetron sputtering process is more favorable for forming a uniform and compact protective layer, so that the increase rate of the interface impedance in the circulating process is kept at a lower level, and the power-assisted sodium metal battery realizes better circulating performance.
5) Comparing the data of examples 1-12 and comparative example 3, it can be seen that: the polyphosphoric acid is used as a protective layer of the sodium metal electrode, and when the polyphosphoric acid is applied to the battery, the interface stability of the battery after circulation is relatively poor, and the sodium metal electrode is protected by the sodium metaphosphate, the sodium pyrophosphate, the sodium phosphate, the sodium tripolyphosphate, the sodium hexametaphosphate and other sodium polyphosphates, so that the polyphosphoric acid is more beneficial to having good circulation stability in the application of the battery. The polyphosphoric acid reacts with sodium metal to cause uneven thickness of a formed protective layer, so that poor interface stability and increased internal resistance of the battery after circulation are finally caused.
In summary, the protection process for the sodium metal cathode is feasible by depositing a protective layer on the surface layer of the sodium metal through vacuum magnetron sputtering. The process regulates and controls the thickness of the protective layer by means of a vacuum magnetron sputtering technology, not only effectively reduces the contact and reaction between the electrolyte and sodium metal, improves the interface stability of the sodium metal, but also avoids the defects of increased internal resistance of the battery and the like caused by uneven film thickness in the conventional protective layer preparation process.
The technical features of the embodiments described above may be arbitrarily combined, and for brevity of description, all possible combinations of the technical features in the embodiments described above are not exhaustive, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention as defined in the following claims.
Claims (10)
1. A protection method of a sodium metal negative electrode is characterized by comprising the following steps: the sodium sheet is used as a substrate, the protective layer is used as a target material, the protective layer is deposited on the surface layer of the sodium metal by utilizing a vacuum magnetron sputtering process, the protection of the sodium metal cathode is realized, and the protective layer is inorganic sodium salt containing a P-O bond.
2. The method for protecting a sodium metal negative electrode according to claim 1, wherein the protective layer is any one selected from the group consisting of sodium metaphosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium hexapolyphosphate, sodium polyphosphate, and sodium phosphate.
3. The method of claim 1, wherein the protective layer is sodium metaphosphate.
4. The method for protecting the sodium metal cathode according to claim 1, wherein the deposition thickness of the protective layer of the sodium metal surface layer is controlled by adjusting the deposition time by using a vacuum magnetron sputtering process, and the deposition thickness of the protective layer is 100-500nm.
5. The method of claim 1, wherein the protective layer is sodium metaphosphate, and the sodium metaphosphate is deposited to a thickness of 200nm.
6. The method of claim 1, wherein the protective layer is sodium tripolyphosphate and the deposition thickness of the sodium tripolyphosphate is 100nm.
7. The method for protecting the sodium metal cathode according to claim 1, wherein the vacuum magnetron sputtering process conditions are as follows: the pressure was-0.1 Kpa and the deposition rate was 100nm/h under an argon atmosphere.
8. A battery, characterized in that the battery comprises a negative electrode, a positive electrode, an electrolyte and a diaphragm, wherein the negative electrode is a sodium metal negative electrode protected by the protection method according to any one of claims 1 to 7.
9. The battery of claim 8, wherein the battery is a CR2032 coin cell battery.
10. The battery of claim 8, wherein the positive electrode comprises NaFePO in a mass ratio 4 SP PVDF = 96; the electrolyte is 1mol/L NaPF 6 Dissolved in DME, and the membrane is a glass fiber membrane.
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| US20200058922A1 (en) * | 2016-11-02 | 2020-02-20 | Vanderbilt University | Electrochemical cells and methods of making and using thereof |
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| US20050186469A1 (en) * | 2001-12-21 | 2005-08-25 | Polyplus Battery Company | Chemical protection of a lithium surface |
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| US20200058922A1 (en) * | 2016-11-02 | 2020-02-20 | Vanderbilt University | Electrochemical cells and methods of making and using thereof |
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