CN117747845A - Sodium metal battery - Google Patents
Sodium metal battery Download PDFInfo
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- CN117747845A CN117747845A CN202311680070.1A CN202311680070A CN117747845A CN 117747845 A CN117747845 A CN 117747845A CN 202311680070 A CN202311680070 A CN 202311680070A CN 117747845 A CN117747845 A CN 117747845A
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- sodium metal
- metal battery
- sodium
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- aluminum foil
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 55
- 239000011888 foil Substances 0.000 claims abstract description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 45
- YVIMHTIMVIIXBQ-UHFFFAOYSA-N [SnH3][Al] Chemical compound [SnH3][Al] YVIMHTIMVIIXBQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 32
- 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 description 31
- 238000007747 plating Methods 0.000 claims description 31
- 229910052708 sodium Inorganic materials 0.000 claims description 31
- 238000009713 electroplating Methods 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000004210 ether based solvent Substances 0.000 claims description 14
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 239000005486 organic electrolyte Substances 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229910001432 tin ion Inorganic materials 0.000 claims description 11
- -1 aluminum ions Chemical class 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 229910020808 NaBF Inorganic materials 0.000 claims description 5
- 229910021201 NaFSI Inorganic materials 0.000 claims description 5
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 5
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 5
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 5
- 229940079864 sodium stannate Drugs 0.000 claims description 5
- 229910001373 Na3V2(PO4)2F3 Inorganic materials 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 16
- 230000008021 deposition Effects 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 210000004027 cell Anatomy 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 9
- 210000001787 dendrite Anatomy 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 7
- 238000007733 ion plating Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000013354 porous framework Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
-
- 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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- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a sodium metal battery, which comprises a positive plate and a negative plate, wherein the negative plate is a negative current collector, and the negative current collector is an aluminum foil layer with an aluminum-tin alloy film layer plated on the surface. The sodium metal battery has the characteristics of good structural flatness, strong processing controllability and high cycle stability.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a sodium metal battery.
Background
In recent decades, lithium ion batteries have been incorporated into people's daily lives and are widely used in the fields of mobile electronic devices and electric automobiles. However, lithium resources are relatively low in reserves on earth and are distributed unevenly throughout the world. In contrast, sodium ion batteries are low cost raw materials and have a similar "rocking chair" reaction mechanism as lithium ion batteries, and therefore are of great interest in the industry as alternatives to lithium ion batteries.
Sodium metal batteries have a higher theoretical specific capacity (1166 mAh/g) and a lower redox potential (-2.714vvs.she). Negative sodium metal-free batteries are considered the best choice because of their higher energy density, lower cost, and easier battery preparation. However, sodium metal batteries are generally faced with the problem that during cycling, side reactions are very likely to occur at the interface between sodium metal and liquid electrolyte to form an unstable solid electrolyte interface film (SEI), the Solid Electrolyte Interface (SEI) film formed continuously can lead to low coulombic efficiency and rapid capacity fade, uneven SEI surface current density and uneven sodium ion distribution, and sodium metal is repeatedly dissolved and deposited on the electrode to easily form uneven holes and dendrites, and uncontrolled sodium dendrite growth can puncture the separator to cause short circuit of the battery, thus causing safety problems.
Compared to conventional sodium metal batteries, non-negative sodium metal batteries need to face greater challenges due to the lack of supplemental sodium on the negative side. In order to solve the above problems, researchers have made various attempts, mainly: (1) Modifying electrolyte to control sodium metal deposition behavior and SEI film components; (2) structural design and surface modification of the current collector; (3) solid state electrolytes are used. As Mo Lijun, the content ratio of two conventional linear ether solvents is adjusted to form a composite electrolyte, and a stable SEI film interface is formed, thereby realizing the efficient sodium deposition/dissolution of the cathodeJ. Am. Chem. Soc.2023, 145, 47, 25643-25652). Fluorinated porous frameworks have been reported as dual functional nucleation/support layers with both high sodium affinity and low sodium reactivity as taught by university of northwest Xu Fei and Wang Hongjiang. The sodium-philic fluorinated edge channels are uniformly dispersed throughout the framework to achieve both uniform metallic sodium nucleation and negligible active sodium consumption. Shows good interfacial stability at high depth of discharge, and the non-negative full cell achieved 400 cycles of stabilization cycles at a current density of 2C (Science Advances, 2023, 9, eadh 8060.). For example, chinese patent application CN113451546A discloses a sodium metal battery and an electrochemical device, wherein the battery comprises a positive electrode plate and a negative electrode plate, the negative electrode plate is a negative electrode current collector, and the thickness of a sodium layer deposited on the negative electrode current collector in situ after the battery is charged and discharged for the first time is more than or equal to 30nm. The method comprisesAccording to the invention, the first irreversible capacity of the positive electrode material and the design optimization of the battery core are utilized, after the battery core is charged and discharged for the first time, the residual sodium metal quantity is enough to uniformly form a sodium deposition layer with a certain thickness on the surface of the negative electrode current collector, so that the higher nucleation energy required by depositing sodium on the surface of the current collector in the subsequent charge and discharge cycle process is avoided, the overall deposition overpotential is reduced, and meanwhile, the deposition uniformity of sodium metal and the reversibility of the charge and discharge process are claimed to be ensured. The negative electrode current collector adopts a surface modification mode to improve sodium deposition/dissolution, specifically, a mode of coating a conductive coating with a certain thickness on the surface, and the mode has the following problems: such as relatively poor adhesion of the conductive coating to the substrate; if the surface of the conductive coating is rugged, sodium is not beneficial to uniform deposition, yi Shengchang dendrites; if sodium is required to deposit a sodium layer with a certain thickness on the surface of the battery after the battery is charged and discharged for the first time, the first effect requirement on the positive electrode is extremely high (because the first effect of the non-negative sodium metal battery is mainly dependent on the first effect of the positive electrode), and the first effect of the positive electrode is excessively high, the sodium metal with a certain thickness is difficult to deposit; too low, the deposited sodium metal layer is too thick, and the technical effect is difficult to ensure.
The results of the researches play a certain role in uniform deposition of sodium metal, and provide a new thought for solving the problem of dendrite growth, however, the preparation methods of the materials are complex in operation and difficult to produce on a large scale. The main preparation is as follows: deposition and dissolution of sodium ions are uneven, and dendrite effect is generated in the circulation process; the SEI film is not compact, side reactions are easy to occur at the interface between metal sodium and liquid electrolyte, and the continuously formed Solid Electrolyte Interface (SEI) film can cause low coulombic efficiency.
Disclosure of Invention
The invention aims to provide a sodium metal battery which has the characteristics of good structural flatness, strong processing controllability and high cycle stability.
The invention can be realized by the following technical scheme:
the invention discloses a sodium metal battery, which comprises a positive plate and a negative plate, wherein the negative plate is a negative current collector, and the negative current collector is an aluminum foil layer with an aluminum-tin alloy film layer plated on the surface.
In the invention, the aluminum tin electroplated layer is very compact and flat, which is beneficial to uniform deposition/dissolution of sodium; the sodium ions deposit as metallic sodium on the aluminum tin electroplated layer with a low overpotential so that sodium deposition/dissolution is more uniform.
Further, the aluminum foil layer plated with the aluminum-tin alloy film layer is prepared by electroplating an aluminum foil layer in a plating solution containing aluminum ions and tin ions.
In the invention, the electroplating mode realizes low-cost large-scale preparation of the modified foil, and has great commercial application prospect; compared with the prior art, the fluorinated porous framework is used as a difunctional nucleation/carrier layer with high sodium affinity and low sodium reactivity, has high cost and is difficult to prepare on a large scale. The invention has the advantages of smooth and compact electroplating surface, high binding force, difficult falling off, small fluctuation of foil thickness variation and no requirement on the anode; compared with the prior art, the coating modification mode has the advantages of larger thickness increase, unfavorable volume energy density surface roughness, low binding force and strict first effect requirement on the positive electrode.
Further, the plating solution comprises the components of a mixed solution of sodium hydroxide, sodium stannate and sodium metaaluminate or a mixed solution of potassium hydroxide, potassium stannate and potassium metaaluminate, the concentration of the plating solution is 0.05-5 mol/L, and the molar ratio of aluminum to tin is 0.1-10. In the invention, the concentration directly influences the thickness of a electroplated layer and the proportion of aluminum and tin in an aluminum-tin alloy layer, different electrolytes are adopted for different positive electrodes, the influence on sodium ion deposition is different, and the proportion of aluminum and tin needs to be regulated and controlled within the control range of the invention to improve the reversibility of sodium deposition/dissolution.
Further, the current density in the electroplating process is 40-150 mA/cm, the thickness of the aluminum-tin alloy film layer is 0.5-2 mu m, and the thickness of the aluminum foil is 7-20 mu m. In the invention, the control of the current density has larger influence on the performance, the current density is too small, the formed electroplated layer has poor compactness and uneven surface, and dendrites are easy to generate in the subsequent battery in the long cycle process; the too high current density can lead to loose plating layers, poor binding force, and the phenomenon of 'scorching' when severe, or dendritic crystals or spongy plating layers can be formed, so that the electroplating fails.
Further, the aluminum foil is soaked for 0.5 to 2 hours with organic acid with the concentration of 0.01 to 0.5mol/L for degreasing treatment before electroplating, and the organic acid is one or more than two of formic acid, acetic acid, propionic acid and/or citric acid. In the invention, the organic acid adopted in the degreasing treatment is weak acid, so that strong acid is avoided, and if strong acid is used, the aluminum foil can be reacted and dissolved; the use of weak acids has the following benefits: 1. removing surface stains; 2. etching the surface of the foil to a certain extent to improve the bonding force between the plating layer and the substrate.
Further, the aluminum foil plated with the aluminum-tin alloy film layer is washed after electroplating and then dried at 50-100 ℃ for standby. In the present invention, the effect of drying temperature on performance is manifested in: the temperature is too low, the drying speed is low, and the improvement of the production efficiency is restricted; the temperature is too high, the plating layer is oxidized, and the conductivity is deteriorated.
Further, the positive plate comprises a positive current collector and a positive active material coated on the surface of the positive current collector, wherein the positive active material is Na 0.44 MnO 2 、Na 3 V 2 (PO 4 ) 3 、Na 3 V 2 (PO 4 ) 2 F 3 And/or Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 。
Further, the sodium metal battery also comprises an organic electrolyte, wherein the organic electrolyte contains disodium salt and ether-based solvent. In the invention, by the system, a better SEI film is formed, so that deposited sodium metal is more stable, and side reactions are reduced.
Further, the disodium salt is NaPF 6 、NaBF 4 Any two of NaFSI and NaTFSI, wherein any concentration is not lower than 0.1mol/L, and the sum of the concentrations is between 0.8 and 1.5 mol/L; the ether-based solvent is one or more of dioxolane, diglyme and/or diglyme.
Further, the formation mode of the sodium metal battery is normal temperature high pressure full electrochemical formation: at normal temperature, the formation pressure is 0.5-8MPa, and the formation process steps are as follows: and charging the constant current of 0.05C for 4h, charging the constant current of 0.1C for 3h, charging the constant current of 0.2C for 2h, and charging the constant current of 0.5C to the cut-off voltage.
The sodium metal battery has the following beneficial effects:
the aluminum foil negative electrode current collector of the surface modified sodium metal battery achieves surface leveling, homogenization and densification through electroplating surface modification, and has good adhesive force between an aluminum tin coating and the surface of the current collector, so that the surface modified aluminum foil negative electrode current collector of the invention has good structural stability, can effectively reduce nucleation overpotential of sodium, simultaneously realizes uniform deposition and dissolution of sodium ions in a charging and discharging process, and inhibits growth of sodium dendrites, thereby avoiding the problems of poor cycling stability, low coulomb efficiency, poor safety performance and the like caused by nonuniform deposition of the sodium ions, improving electrochemical performance of the battery, and enabling the whole sodium battery system to have higher energy density without the negative electrode battery system with additional sodium metal. The preparation method of the surface modified aluminum foil negative electrode current collector of the negative electrode-free sodium metal battery has the advantages of simple process, good repeatability and easy realization of large-scale industrial production.
Drawings
FIG. 1 is a view of Na of example 1 4 Fe 3 (PO 4 ) 2 P 2 O 7 The first week of the full battery without negative sodium metal is charged and discharged;
FIG. 2 is a view of Na of example 1 4 Fe 3 (PO 4 ) 2 P 2 O 7 And (3) a full cell cycle performance curve without negative sodium metal.
Detailed Description
In order to better understand the technical solution of the present invention, the following describes the product of the present invention in further detail with reference to examples.
The invention discloses a sodium metal battery, which comprises a positive plate and a negative plate, wherein the negative plate is a negative current collector, and the negative current collector is an aluminum foil layer with an aluminum-tin alloy film layer plated on the surface.
Further, the aluminum foil layer plated with the aluminum-tin alloy film layer is prepared by electroplating an aluminum foil layer in a plating solution containing aluminum ions and tin ions.
Further, the plating solution comprises the components of a mixed solution of sodium hydroxide, sodium stannate and sodium metaaluminate or a mixed solution of potassium hydroxide, potassium stannate and potassium metaaluminate, the concentration of the plating solution is 0.05-5 mol/L, and the molar ratio of aluminum to tin is 0.1-10.
Further, the current density in the electroplating process is 40-150 mA/cm, the thickness of the aluminum-tin alloy film layer is 0.5-2 mu m, and the thickness of the aluminum foil is 7-20 mu m.
Further, the aluminum foil is soaked for 0.5 to 2 hours with organic acid with the concentration of 0.01 to 0.5mol/L for degreasing treatment before electroplating, and the organic acid is one or more than two of formic acid, acetic acid, propionic acid and/or citric acid.
Further, the aluminum foil plated with the aluminum-tin alloy film layer is washed after electroplating and then dried at 50-100 ℃ for standby.
Further, the positive plate comprises a positive current collector and a positive active material coated on the surface of the positive current collector, wherein the positive active material is Na 0.44 MnO 2 、Na 3 V 2 (PO 4 ) 3 、Na 3 V 2 (PO 4 ) 2 F 3 And/or Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 。
Further, the sodium metal battery also comprises an organic electrolyte, wherein the organic electrolyte contains disodium salt and ether-based solvent.
Further, the disodium salt is NaPF 6 、NaBF 4 Any two of NaFSI and NaTFSI, wherein any concentration is not lower than 0.1mol/L, and the sum of the concentrations is between 0.8 and 1.5 mol/L; the ether-based solvent is one or more of dioxolane, diglyme and/or diglyme.
Further, the formation mode of the sodium metal battery is normal temperature high pressure full electrochemical formation: at normal temperature, the formation pressure is 0.5-8MPa, and the formation process steps are as follows: and charging the constant current of 0.05C for 4h, charging the constant current of 0.1C for 3h, charging the constant current of 0.2C for 2h, and charging the constant current of 0.5C to the cut-off voltage.
Example 1
The sodium metal battery of this example was prepared and tested as follows: firstly, soaking a 16 mu m aluminum foil in a 0.01mol/L citric acid solution for 0.5h, and then washing with deionized water for three times; then 0.2mol/L aluminum is addedElectroplating with current density of 80 mA/cm in ion and 1mol/L tin ion plating solution to obtain a plating layer with thickness of 1.5 μm, cleaning with deionized water, and baking at 80deg.C for 1 hr to obtain the surface modified aluminum foil current collector. Na is used as positive electrode 4 Fe 3 (PO 4 ) 2 P 2 O 7 Glassfiber (GF/D) as membrane and electrolyte 0.7 mol/L NaPF 6 +0.3 mol/L NaTFSI+1: DME/DOL with 1 volume ratio is used for assembling the full battery, the full battery is charged to 3.5V according to the formation step 0.05C 4h,0.1C 3h,0.2C 2h,0.5C of 6MPa at room temperature, and then tested between 2.5 and 3.5V.
The first-week charge-discharge curve is shown in FIG. 1, the first-week coulomb efficiency is 84.7%, and the specific discharge capacity is 97.34 mAh/g. As can be seen from fig. 2, the assembled full cell was pre-cycled for 3 cycles at a current density of 0.2C and a voltage interval of 2.5-3.5V, and then cycled for 600 times at a current density of 1C and a voltage interval of 2.5-3.5V, while maintaining a coulombic efficiency of 99.6% and above, with a capacity retention of greater than 95%, exhibiting excellent electrochemical stability.
Example 2
The sodium metal battery of this example was prepared and tested as follows: firstly, soaking a 16 mu m aluminum foil in a formic acid solution with the concentration of 0.02mol/L for 1h, and then washing with deionized water for three times; then the aluminum foil is put into 0.1mol/L aluminum ion and 0.1mol/L tin ion plating solution, and is electroplated with current density of 100mA/cm to obtain a plating layer with thickness of 1 mu m, and the aluminum foil is baked for 1h at 80 ℃ after being cleaned by deionized water, thus obtaining the surface modified aluminum foil current collector. Na is used as positive electrode 3 V2(PO 4 ) 3 Glassfiber (GF/D) as membrane with electrolyte of 0.5mol/L NaPF 6 +0.8 mol/L NaTFSI 1: d DME/DOL with 1 volume ratio, the assembled full cell is charged to 3.6V according to the formation step 0.05C 4h,0.1C 3h,0.2C 2h,0.5C of 2MPa at room temperature, and then tested between 2.7 and 3.6V. The initial coulomb efficiency was 96.7%, and the specific discharge capacity was 107.34 mAh/g. The assembled full cell is pre-cycled for 3 circles under the current density of 0.2C and the voltage interval of 2.7-3.6V, and then is cycled for 800 times under the current density of 1C and the voltage interval of 2.7-3.6V, the coulombic efficiency of 99.6 percent and above is still maintained, the capacity retention rate is more than 94 percent, and the excellent performance is shownElectrochemical stability.
Example 3
The sodium metal battery of this example was prepared and tested as follows: firstly, immersing a 12 mu m aluminum foil in 0.01mol/L acetic acid solution for 1.5 hours, and then washing with deionized water for three times; then the aluminum foil is put into 0.8mol/L aluminum ion and 1.9mol/L tin ion plating solution, and is electroplated with current density of 110mA/cm to obtain a plating layer with thickness of 0.8 mu m, and the aluminum foil is baked for 1h at 80 ℃ after being cleaned by deionized water, thus obtaining the surface modified aluminum foil current collector. Na is used as positive electrode 4 Fe 3 (PO 4 ) 2 P 2 O 7 Glassfiber (GF/D) as membrane with electrolyte of 1mol/L NaPF 6 +0.2 mol/L NaBF 4 +1: 1. the volume ratio DED/DOL, the assembled full cell was charged to 3.5V at room temperature according to a pressure of 1MPa in a chemical process step 0.05C 4h,0.1C 3h,0.2C 2h,0.5C, and then tested between 2.5 and 3.5V. The initial coulomb efficiency was 85.7%, and the specific discharge capacity was 98.66 mAh/g. As can be seen from fig. 2, the assembled full cell was pre-cycled for 3 cycles at a current density of 0.2C and a voltage interval of 2.5-3.5V, and then cycled for 600 times at a current density of 1C and a voltage interval of 2.5-3.5V, while maintaining a coulombic efficiency of 99.6% and above, with a capacity retention of greater than 96%, exhibiting excellent electrochemical stability.
The results show that the sodium metal is uniformly deposited/dissolved on the surface of the electroplating surface modified current collector, so that the growth of sodium dendrite is effectively inhibited, the electrochemical reaction kinetics is enhanced, and excellent electrochemical performance is shown.
The invention adopts electroplating to carry out surface modification on the negative aluminum foil, has strong process controllability, high plating flatness and high compactness, and is suitable for effectively ensuring that the negative current collector is used as a pole piece without a negative electrode; the pretreatment mode of the aluminum foil before electroplating is weak acid soaking and cleaning, and strict requirements are imposed on the type, concentration and time of acid; the plating solution is a mixed solution of concentration limiting aluminum ions and tin ions; the electroplating current density in the invention has specific requirements, and the current density directly influences the compactness, uniformity and flatness of the plating layer, thereby influencing the subsequent deposition and dissolution of sodium ions. The cathode-free sodium metal battery is fully electrified at normal temperature and high pressure, so that the formed SEI film is more stable and compact, and is beneficial to long-cycle
Example 4
The sodium metal battery method of this example is as follows: firstly, soaking a 20 mu m aluminum foil in a 0.3mol/L formic acid solution for 0.5h, and then washing with deionized water for three times; then placing the aluminum ion and tin ion plating solution, electroplating with current density of 150mA/cm to obtain a plating layer with thickness of 0.5-2 mu m, cleaning with deionized water, and baking at 80 ℃ for 1h to obtain the surface modified aluminum foil current collector. Na is used as positive electrode 0.44 MnO 2 Glassfiber (GF/D) was used as a separator, and an electrolyte was added to assemble a full cell.
Specifically, the plating solution comprises the components of a mixed solution of sodium hydroxide, sodium stannate and sodium metaaluminate, the concentration of the plating solution is 5mol/L, and the molar ratio of aluminum to tin is 5.
Specifically, the sodium metal battery further comprises an organic electrolyte, wherein the organic electrolyte contains disodium salt and an ether-based solvent. Disodium salt is NaPF 6 、NaBF 4 Wherein, any concentration is not lower than 0.1mol/L, and the sum of the concentrations is 1.5 mol/L; the ether-based solvent is dioxolane or diglyme.
Example 5
The sodium metal battery method of this example is as follows: firstly, immersing 10 mu m aluminum foil in 0.01mol/L acetic acid and propionic acid solution for 2 hours, and then washing with deionized water for three times; then placing the aluminum ion and tin ion plating solution, electroplating with current density of 100mA/cm to obtain a plating layer with thickness of 0.5 mu m, cleaning with deionized water, and baking at 100 ℃ for 1h to obtain the surface modified aluminum foil current collector. Na is used as positive electrode 3 V 2 (PO 4 ) 3 Glassfiber (GF/D) was used as a separator, and an electrolyte was added to assemble a full cell.
Specifically, the plating solution comprises a mixed solution of potassium hydroxide, potassium stannate and potassium metaaluminate, the concentration of the plating solution is 2mol/L, and the molar ratio of aluminum to tin is 0.1.
Specifically, the sodium metal battery further comprises an organic electrolyte, wherein the organic electrolyte contains disodium salt and an ether-based solvent. Disodium salt is NaPF 6 NaTFSI, where any concentration is not lower than0.1mol/L, and the concentration sum is between 1.2 mol/L; the ether-based solvent is dioxolane or diethylene glycol dimethyl ether.
Example 6
The sodium metal battery method of this example is as follows: firstly, soaking a 7 mu m aluminum foil in 0.5mol/L propionic acid and citric acid solution for 1h, and then washing with deionized water for three times; then placing the aluminum ion and tin ion plating solution, electroplating with 40mA/cm current density to obtain a plating layer with the thickness of 2 mu m, cleaning with deionized water, and baking at 80 ℃ for 1h to obtain the surface modified aluminum foil current collector. Na is used as positive electrode 3 V 2 (PO 4 ) 2 F 3 Glassfiber (GF/D) was used as a separator, and an electrolyte was added to assemble a full cell.
Specifically, the plating solution comprises the components of a mixed solution of sodium hydroxide, sodium stannate and sodium metaaluminate, the concentration of the plating solution is 0.05mol/L, and the molar ratio of aluminum to tin is 10.
Specifically, the sodium metal battery further comprises an organic electrolyte, wherein the organic electrolyte contains disodium salt and an ether-based solvent. The disodium salt is NaFSI and NaTFSI, wherein any concentration is not lower than 0.1mol/L, and the sum of the concentrations is 0.8 mol/L; the ether-based solvent is dioxolane, diglyme or diglyme.
Example 7
The sodium metal battery method of this example is as follows: firstly, soaking an aluminum foil with the diameter of 13 mu m in formic acid, acetic acid, propionic acid and citric acid solution with the concentration of 0.1mol/L for 1.5 hours, and then washing the aluminum foil with deionized water for three times; then placing the aluminum ion and tin ion plating solution, electroplating with current density of 90mA/cm to obtain a plating layer with thickness of 1.5 mu m, cleaning with deionized water, and baking at 70 ℃ for 1h to obtain the surface modified aluminum foil current collector. Positive electrode use or Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Glassfiber (GF/D) was used as a separator, and an electrolyte was added to assemble a full cell.
Specifically, the plating solution comprises a mixed solution of potassium hydroxide, potassium stannate and potassium metaaluminate, the concentration of the plating solution is 2mol/L, and the molar ratio of aluminum to tin is 4.
Specifically, the sodium metal battery also comprises an organic electrolyte, wherein the organic electrolyte containsDisodium salts and ether-based solvents. Disodium salt is NaPF 6 NaFSI, wherein any concentration is not lower than 0.1mol/L, and the sum of the concentrations is 1.1 mol/L; the ether-based solvent is dioxolane or diglyme.
The foregoing examples are merely exemplary embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and that these obvious alternatives fall within the scope of the invention.
Claims (10)
1. The utility model provides a sodium metal battery, includes positive plate, negative plate, its characterized in that: the negative plate is a negative current collector, and the negative current collector is an aluminum foil layer with an aluminum-tin alloy film layer plated on the surface.
2. The sodium metal battery of claim 1, wherein: the aluminum foil layer plated with the aluminum-tin alloy film layer is prepared by electroplating an aluminum foil in a plating solution containing aluminum ions and tin ions.
3. The sodium metal battery according to claim 2, wherein: the plating solution comprises the components of a mixed solution of sodium hydroxide, sodium stannate and sodium metaaluminate or a mixed solution of potassium hydroxide, potassium stannate and potassium metaaluminate, wherein the concentration of the plating solution is 0.05-5 mol/L, and the molar ratio of aluminum to tin is 0.1-10.
4. A sodium metal battery according to claim 3, wherein: the current density in the electroplating process is 40-150 mA/cm, the thickness of the aluminum-tin alloy film layer is 0.5-2 mu m, and the thickness of the aluminum foil is 7-20 mu m.
5. The sodium metal battery according to claim 4, wherein: the aluminum foil is subjected to oil removal treatment by soaking with organic acid with the concentration of 0.01-0.5 mol/L for 0.5-2h before electroplating, wherein the organic acid is one or more of formic acid, acetic acid, propionic acid and/or citric acid.
6. The sodium metal battery according to claim 5, wherein: the aluminum foil plated with the aluminum-tin alloy film layer is washed after electroplating and then dried at 50-100 ℃ for standby.
7. The sodium metal battery of claim 1, wherein: the positive plate comprises a positive current collector and a positive active material coated on the surface of the positive current collector, wherein the positive active material is Na 0.44 MnO 2 、Na 3 V 2 (PO 4 ) 3 、Na 3 V 2 (PO 4 ) 2 F 3 And/or Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 。
8. The sodium metal battery of claim 1, wherein: the sodium metal battery also includes an organic electrolyte containing a disodium salt and an ether-based solvent.
9. The sodium metal battery according to claim 8, wherein: the disodium salt is NaPF 6 、NaBF 4 Any two of NaFSI and/or NaTFSI, wherein any concentration is not lower than 0.1mol/L, and the sum of the concentrations is between 0.8 and 1.5 mol/L; the ether solvent is one or more of dioxolane, diglyme and/or diglyme.
10. The sodium metal battery of claim 1, wherein: the formation mode of the sodium metal battery is normal-temperature high-pressure full electrochemical formation: at normal temperature, the formation pressure is 0.5-8MPa, and the mixture is charged to the cut-off voltage.
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| CN117977115A (en) * | 2024-03-28 | 2024-05-03 | 西北工业大学 | Battery diaphragm capable of inhibiting growth of sodium dendrite and preparation method and application thereof |
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| CN117977115A (en) * | 2024-03-28 | 2024-05-03 | 西北工业大学 | Battery diaphragm capable of inhibiting growth of sodium dendrite and preparation method and application thereof |
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