CN109888193B - Method for improving electrodeposition and dissolution reversibility of sodium metal negative electrode - Google Patents
Method for improving electrodeposition and dissolution reversibility of sodium metal negative electrode Download PDFInfo
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- CN109888193B CN109888193B CN201910031215.2A CN201910031215A CN109888193B CN 109888193 B CN109888193 B CN 109888193B CN 201910031215 A CN201910031215 A CN 201910031215A CN 109888193 B CN109888193 B CN 109888193B
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- 238000004090 dissolution Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 27
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 22
- 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 21
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 239000011859 microparticle Substances 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims description 21
- 230000008021 deposition Effects 0.000 claims description 21
- 238000005275 alloying Methods 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 2
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 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 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001291 vacuum drying 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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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
本发明公开了一种提高钠金属负极电沉积和溶出可逆性的方法，包括如下步骤：(1)将可以与钠产生合金的金属M的纳米粒子或微米粒子负载于不与Na产生合金的金属N材质的集流体表面，制成极片；(2)以上述极片为工作电极，以Na片为对电极和参比电极，配合电解液和隔膜组装成电池，控制Na的溶出截止电位低于Na在Na‑金属M合金的脱合金起始电位，以2mAcm‑2的电流密度进行电化学沉积和溶出循环。本发明通过构建一个能与钠合金化的集流体，可以实现钠金属在2mAcm‑2的电流下，高效稳定的循环1700‑2000圈，平均库伦效率99.9％，可以促进钠金属电池的商业应用，为移动电子设备和电动汽车等的储能系统提供了一个廉价且高容量的负极。
The invention discloses a method for improving the reversibility of electrodeposition and dissolution of sodium metal negative electrode, comprising the following steps: (1) loading nano-particles or micro-particles of metal M that can be alloyed with sodium on a metal that does not alloy with Na The surface of the current collector made of N material is made into a pole piece; (2) the above pole piece is used as the working electrode, the Na piece is used as the counter electrode and the reference electrode, and the battery is assembled with the electrolyte and the diaphragm to control the low dissolution cut-off potential of Na. Electrochemical deposition and dissolution cycles were performed at a current density of 2 mAcm -2 at the onset potential of the dealloying of Na in Na-metal M alloys. By constructing a current collector that can be alloyed with sodium, the present invention can realize high-efficiency and stable cycling of sodium metal for 1700-2000 cycles at a current of 2 mAcm-2, and an average Coulomb efficiency of 99.9%, which can promote the commercial application of sodium metal batteries. It provides an inexpensive and high-capacity anode for energy storage systems such as mobile electronic devices and electric vehicles.
Description
Technical Field
The invention belongs to the technical field of energy storage, and particularly relates to a method for improving electrodeposition and dissolution reversibility of a sodium metal cathode.
Background
The energy storage technology with high specific capacity and low cost has great significance for meeting the development of electric vehicles and smart power grids. The sodium metal cathode is an important choice in the design of the next generation of batteries due to the advantages of high theoretical capacity, abundant crustal storage, low price and the like. However, the reversibility of the cycle is poor due to dendritic growth of Na metal during deposition and high chemical reactivity of Na metal to the electrolyte, which severely hampers its application. Studies on room temperature sodium metal anodes have been relatively rare and have been concentrated in the last two or three years.
Methods for improving the electrodeposition and dissolution reversibility of the sodium metal negative electrode can be classified into the following aspects:
1) selection of electrolyte: when using 1M NaPF6When the sodium metal is dissolved in an ether solvent as an electrolyte, the sodium metal can be efficiently deposited and dissolved out on the Cu foil; when high-concentration NaFSI is dissolved in DME as electrolyte, high-efficiency deposition and dissolution of Na metal on the Cu foil can be realized.
2) Improvement of solid electrolyte membrane: an ultrathin inert protective layer with good mechanical properties is formed on the surface of the sodium metal by a physical or chemical method to serve as an artificial SEI film, so that the cycling stability of the sodium metal cathode can be improved; additives such as Na2S60.01M KTFSI was also reported to improve Na metal cycling stability.
3) Designing a current collector: such as porous aluminum, porous copper arrays, different types of carbon materials and the like, can reduce the real current density of Na deposition, provide partial space for Na deposition and reduce the generation of Na dendrites. In addition, elements such as N, S, O and the like are doped in the carbon material, so that sodium-philic sites can be provided, the nucleation barrier of Na deposition is reduced, and the uniformity of Na deposition is improved. The ultra-thin Au layer is sputtered on the Cu foil before the group of subjects, so that the sodium nucleation barrier can be reduced, and the sodium deposition and dissolution efficiency can be improved in a shorter time.
However, the methods in the prior art have relatively limited improvement on the reversibility of the sodium metal negative electrode, and can be circulated more efficiently in a short time under a small current.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for improving the electrodeposition and dissolution reversibility of a sodium metal negative electrode.
The specific principle of the invention is as follows:
na is on electrodes such as Sn and Sb, and a Na-M (Sn, Sb) alloy layer is formed through an alloying reaction before Na deposition occurs. The alloy layer has good sodium affinity, the alloy sodium affinity layer has larger binding force with sodium, the nucleation overpotential of sodium deposition can be reduced, the morphology of sodium deposition is further improved, the sodium deposition and dissolution efficiency is improved, and the Na-M alloy substrate becomes a sodium affinity substrate. Further research has found that a problem limiting the deposition and dissolution cycle life of sodium on such sodium-philic substrates is the repeated alloying and dealloying reactions during the cycle causing the alloy layer to powderize off the current collector. Therefore, by controlling the dissolution potential of sodium, the sodium-philic substrate is stabilized from the second cycle without undergoing alloying and dealloying processes, and the service life of the sodium-philic substrate can be significantly improved.
The technical scheme of the invention is as follows:
a method for improving the electro-deposition and dissolution reversibility of a sodium metal cathode comprises the following steps:
(1) loading nano particles or micro particles of metal M capable of generating alloy with sodium on the surface of a current collector made of metal N material not generating alloy with Na to prepare a pole piece;
(2) the pole piece is taken as a working electrode, a Na piece is taken as a counter electrode and a reference electrode, the battery is assembled by matching with electrolyte and a diaphragm, the dissolution cut-off potential of Na is controlled to be lower than the dealloying initial potential of Na in Na-metal M alloy, and the dissolution cut-off potential is controlled to be 2mAcm-2The current density of the electrode plate is subjected to electrochemical deposition and dissolution circulation, in the process, before Na deposition, Na firstly forms a Na-metal M alloy layer through alloying reaction only in the first circulation, and the subsequent circulation does not generate alloying and dealloying processes, so that the electrode plate is stabilized, and finally the cycle life of Na deposition dissolution reaches 1700-2000 circles.
In a preferred embodiment of the present invention, the metal M includes Sn and Sb.
More preferably, the elution cut potential of Na is less than 0.15V.
In a preferred embodiment of the present invention, the metal N includes Cu, a1 and Ni.
In a preferred embodiment of the present invention, the metal M is supported on the surface of the current collector by a binder.
Further preferably, the mass ratio of the metal M to the binder is 90-100: 5-10.
Further preferably, the binder is sodium carboxymethyl cellulose.
In a preferred embodiment of the invention, the electrolyte is 1M NaOTf-diglyme-0.01M NaTFSI.
In a preferred embodiment of the invention, the separator is of the type Celgard 2400.
The invention has the beneficial effects that: the invention can realize that the sodium metal is at 2mAcm by constructing a current collector capable of alloying with sodium-2Under the current of (1), the circulation is efficiently and stably performed for 1700-2000 circles, the average coulombic efficiency is 99.9%, the commercial application of the sodium metal battery can be promoted, and a cheap and high-capacity cathode is provided for energy storage systems of mobile electronic equipment, electric automobiles and the like.
Drawings
Fig. 1 is a photograph of a current collector fabricated in example 1 of the present invention: optical photographs of the physically sputtered Sn and Sb are a and b, respectively, and scanning electron micrographs are c and d, respectively; optical images of SnNPs and Sb MPs fixed to the Cu foil with a binder are e and f, respectively, and scanning electron micrographs are g and h, respectively.
FIG. 2: is a Cyclic Voltammogram (CV) of the current collector manufactured in example 1 of the present invention: the cyclic voltammograms of Sn and Sb are respectively as indicated by the symbols in the figure.
Fig. 3 is a graph of the cycle efficiency under the control of the method in example 1 of the present invention, where a is the cycle efficiency of Na deposition dissolution on the two current collectors of Sn film and Sn NPs that are physically sputtered, and b is the cycle efficiency of Na deposition dissolution on the two current collectors of Sb film and Sb MPs that are physically sputtered under the control of the method in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
Sn with the thickness of 50nm is sputtered on copper foil by a magnetron sputtering method to form a pole piece, as shown in figure 1, on an optical photo, the surface of the pole piece can be seen to be blue, and a thin layer can also be seen from a scanning electron microscope. The electrode plate is used as a working electrode, and a sodium plate is used as a counter electrode and a reference electrode to assemble the CR2032 type button cell. The electrolyte is 1MNaOTf-diglyme-0.01M NaTFSI, and the diaphragm is Celgard 2400 type.
When the button cell is used for cyclic voltammetry experiments, as seen from a cyclic voltammogram shown in fig. 2, Na not only has sodium deposition and dissolution reaction on Sn and Sb electrodes, but also has alloying and dealloying processes. The dealloying onset potentials of Na on Sn and Sb were 0.15 and 0.60V, respectively.
At a distance of 2mAcm-2The electrochemical deposition and dissolution cycle are carried out, two dissolution cut-off potentials of 0.10 and 1.00V are set, and as can be seen from figure 3a, the stable cycle can be only carried out for 800 circles when the dissolution potential of sodium is controlled to 1.00V, and the stable cycle can be 600 circles when the dissolution potential is controlled to 0.10V. This is mainly because, when the stripping potential is set to 1.00V, not only the deposition and stripping reaction of sodium but also the sodium alloy and dealloying reaction occur per cycle, and the repeated alloying/dealloying process causes the Sn layer to fall off from the Cu foil surface; when the dissolution cut-off potential is set to be 0.10V, the potential is lower than the initial potential of 0.12V of sodium which is removed from Na-Sn, so that the alloying process is only generated in the first cycle, and the alloying and dealloying processes are not generated in the subsequent cycles, thereby stabilizing the pole piece.
Further, the physically sputtered Sn layer is replaced with Sn Nanoparticles (NPs), and the Sn NPs are fixed in the form of a binder. It was found that at a dissolution potential of 0.10V, the cycle life of sodium deposition dissolution could be further extended to 2000 cycles.
The electrode sheet is specifically prepared by mixing commercial Sn NPs or Sb (micro-meters, MPs) and carboxymethyl cellulose sodium (CMC) as binder at a mass ratio of 92: 8, stirring for 6h, coating the prepared slurry on the surface of copper foil (Cu), and vacuum drying at 120 deg.C for 12 h. The loading capacity of SnNPs or Sb MPs is 0.5mgcm-2As shown in FIGS. 1e and g, the prepared pole piece has a uniform dark black layer on the surface of the copper foil when viewed on an optical photo, and obvious nanoparticles with the diameter of about 150am can be seen on a scanning electron microscope.
Similarly, the same comparison was made with inexpensive Sb. As shown in fig. 3b, it was found that Na could be deposited for 200 dissolution cycles at a 1.00V cut-off on sputtered Sb films; and when the cut-off potential is controlled to be 0.10V, Na can be stably deposited and dissolved for 800 circles. When commercial Sb Micro Particles (MPs) were used instead of physically sputtered Sb, Na was stable deposited at 0.10V cutoff voltage for 1700 cycles.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (6)
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| CN113451546B (en) * | 2021-06-26 | 2022-05-06 | 宁德时代新能源科技股份有限公司 | Sodium metal battery and electrochemical device |
| CN113437254B (en) * | 2021-06-26 | 2022-05-06 | 宁德时代新能源科技股份有限公司 | Negative pole piece of sodium ion battery, electrochemical device and electronic equipment |
| CN113707850A (en) * | 2021-08-30 | 2021-11-26 | 清华大学深圳国际研究生院 | Anode and preparation method thereof, and sodium metal full cell |
| CN117727948B (en) * | 2024-02-07 | 2024-05-14 | 深圳海辰储能科技有限公司 | Negative electrode current collector and preparation method thereof, sodium secondary battery, and electrical equipment |
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