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WO2016002194A1 - Additifs pour électrolyte pour stabilisation d'électrodes en cyanométallate d'un métal de transition - Google Patents

Additifs pour électrolyte pour stabilisation d'électrodes en cyanométallate d'un métal de transition Download PDF

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Publication number
WO2016002194A1
WO2016002194A1 PCT/JP2015/003261 JP2015003261W WO2016002194A1 WO 2016002194 A1 WO2016002194 A1 WO 2016002194A1 JP 2015003261 W JP2015003261 W JP 2015003261W WO 2016002194 A1 WO2016002194 A1 WO 2016002194A1
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battery
electrolyte
tmcm
combinations
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Yuhao Lu
Long Wang
Sean Vail
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Sharp Corp
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Sharp Corp
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Priority claimed from US14/320,352 external-priority patent/US9620815B2/en
Application filed by Sharp Corp filed Critical Sharp Corp
Priority to CN201580035681.8A priority Critical patent/CN106688133A/zh
Publication of WO2016002194A1 publication Critical patent/WO2016002194A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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

Definitions

  • This invention generally relates to electrochemical cells and, more particularly, to an electrolyte containing additives useful for stabilizing transition metal cyanometallate batteries.
  • Transition metal cyanometallates with large interstitial spaces have been investigated as the cathode material for rechargeable lithium-ion batteries [NPL1, NPL2], sodium-ion batteries [NPL3, NPL4], and potassium-ion batteries [NPL5].
  • NPL1, NPL2 lithium-ion batteries
  • NPL3, NPL4 sodium-ion batteries
  • NPL5 potassium-ion batteries
  • Cu,Ni copper and nickel hexacyanoferrates
  • the materials within the aqueous electrolyte demonstrated low capacities and energy densities because: (1) just one sodium-ion can be inserted/extracted into/from per Cu-HCF or Ni-HCF formula, and (2) these transition metal cyanoferrate (TM-HCF) electrodes must be operated below 1.23 V due to the water electrochemical window.
  • the electrochemical window of a substance is the voltage range between which the substance is neither oxidized nor reduced. This range is important for the efficiency of an electrode, and once out of this range, water becomes electrolyzed, spoiling the electrical energy intended for another electrochemical reaction.
  • Mn-HCF manganese hexacyanoferrate
  • Fe-HCF iron hexacyanoferrate
  • TMHCF electrode the actual capacity of a TMHCF electrode is by far smaller than the theoretical value.
  • the theoretical capacity for Mn-HCF is 170 mAh/g, but the reported capacity was just ⁇ 120 mAh/g, as tested in a sodium-ion battery.
  • the capacity difference could be ascribed to the structures and compositions of TMHCFs.
  • Buser, et al. [NPL11] investigated the crystal structure of Prussian Blue (PB), Fe 4 [Fe(CN) 6 ] 3 . xH 2 O and found that Fe(CN) 6 positions were only partly occupied. The vacancies led to water entering the PB interstitial space and even associating with Fe(III) in the lattice [NPL12].
  • the vacancies and water both act to reduce the concentration of mobile ions in the interstitial space of TMHCF.
  • Matsuda, et al. [NPL9] preferred to use A 4x-2 M A [M B (CN) 6 ] x . zH 2 O as a replacement to the nominal formula of A 2 M A M B (CN) 6 because of the vacancies.
  • the vacancies result in dense defects on the surface of TMHCFs. Without interstitial ions and supporting water, the surface easily collapses. The surface degradation can be aggravated when the interstitial ions in the vicinity of the surface are extracted out during electrochemical reactions. In a battery, such degradation leads to poor capacity retention.
  • the surface of the Cu-HCF electrode was modified and its stability was improved.
  • the undercoordinated transition metal (UTM) on the surface retards charge transfer between the TMHCF electrode and electrolyte due to charge repulsion between the UTM and the mobile ions, which may result in poor rate performance.
  • Park, et al. [NPL14] mentioned the surface effect on a LiFePO 4 electrode with undercoordinated Fe 2+ /Fe 3+ at the surface creating a barrier for Li + transport across the electrolyte/electrode interface.
  • some researchers have optimized the synthesis of TMHCFs to reduce defects and vacancies on their surfaces and in the bulk of the material [NPL15, NPL16]. These defect-free TMHCFs demonstrated a longer cycle life.
  • Transition metal cyanometallate (TMCM) electrodes in metal-ion batteries have demonstrated good performance, as indicated by high energy density, high power density, and low cost.
  • TMCM Transition metal cyanometallate
  • defects and vacancies produced in the TMCM electrodes cause structural degradation, which limits their cycle life.
  • Electrolyte additives that can interact and coordinate metal ions around these defects and vacancies to support the structures of the TMCM, enabling a longer cycle lifetime.
  • a method for the self-repair of a TMCM battery electrode is made from a TMCM cathode, an anode, and an electrolyte including a solution made up of a solvent and an alkali or alkaline earth salt.
  • the electrolyte also includes an additive represented as G-R-g:
  • G and g are independently selected from materials that include the elements of nitrogen (N) sulfur (S), and oxygen (O), or combinations of the above-recited elements; and,
  • R is an alkene or alkane group.
  • the method In response to charging and discharging the battery in a plurality of cycles, the method creates vacancies in a surface of the TMCM cathode. Then, the method fills the vacancies in the surface of the TMCM cathode with the electrolyte additive.
  • the solvent may be water, carbonates, furan, oxane, ether, ketone, ester, amide, acetate, siloxane, or combinations thereof.
  • Some examples of the salt include A x Cl, A x SO 4 , A x NO 3 , A x PO 4 ,A x Br, A x I, A x AlO 2 , A x Ac(acetate), A x PF 6 , A x BF 6 , A x ClO 4 , A x AsF 6 , A x AlCl 4 , A x B 5 Cl 5 , A x CF 3 SO 3 , A x (CF 3 SO 2 ) 2 N, and A x (C 2 F 5 SO 2 ) 2 N, where “A” is either an alkali or alkaline earth element.
  • the R alkene/alkane may be formed with a substation such as oxygen, silicon, fluorine, chlorine, phosphorus, aluminum, arsenic, selenium, bromine, or combinations thereof.
  • G and g are independently selected from an alkene or alkane group.
  • the TMCM cathode is expressed by the formula B n M1 p M2 q (CN) r . fH 2 O;
  • M1 and M2 are independently selected from transition metals
  • n is in a range of 0 to 2;
  • f is in a range of 0 to 20;
  • the anode can be made from carbonaceous materials, alkali metals, alkaline earth metals, alloys including tin, alloys including lead, alloys including silicon, alloys including phosphorous, alloys including germanium, titanates including alkali metals, titanates including alkaline earth metals, or combinations thereof.
  • additives could be included in an electrolyte that would interact and coordinate with surface of TMCM electrodes, to cure and reduce the defects and undercoordinated metal-ions, and to improve the cycle lifetime.
  • Fig. 1 is a partial cross-sectional view of an electrolyte for use in a battery with transition metal cyanometallate (TMCM) electrodes.
  • Fig. 2 is a partial cross-sectional view of a TMCM electrode battery.
  • Fig. 3A depicts a fresh TMCM electrode immersed in an electrolyte containing additives.
  • Fig. 3B depicts additives interacting or coordinating with defects on the surface of TMCM electrode to stabilize its structure.
  • Fig. 4A is an example of a Prussian White (PW, Na 2 Fe 2 (CN) 6 ) electrode where no electrolyte additive has been used, showing capacity vs. cycles.
  • Fig. 1 is a partial cross-sectional view of an electrolyte for use in a battery with transition metal cyanometallate (TMCM) electrodes.
  • Fig. 2 is a partial cross-sectional view of a TMCM electrode battery.
  • Fig. 3A depicts a fresh
  • FIG. 4B is an example of a Prussian White (PW, Na 2 Fe 2 (CN) 6 ) electrode where no electrolyte additive has been used, showing capacity vs. voltage.
  • Fig. 5A is an example of the PW electrode where any electrolyte additive has been used, showing capacity vs. cycles .
  • Fig. 5B is an example of the PW electrode where any electrolyte additive has been used, showing capacity vs. voltage.
  • Fig. 6 is a graph comparing the PW electrodes, with and without the ADN additive.
  • Fig. 7 is a flowchart illustrating a method for self-repairing a TMCM battery electrode.
  • Fig. 1 is a partial cross-sectional view of an electrolyte for use in a battery with transition metal cyanometallate (TMCM) electrodes.
  • the electrolyte 100 comprises a solution 102 including a solvent 104 and a salt that can be either an alkali or alkaline earth salt.
  • the salt is represented using reference designator 106.
  • the electrolyte 100 also includes an additive, represented with reference designator 108, comprising G-R-g:
  • G and g are independently selected from a group of materials that include the element of nitrogen (N) sulfur (S), oxygen (O), or combinations of the above-recited elements.
  • R is an alkene or alkane group.
  • independently selected means that an element selected for G may, or may not be an element selected for g.
  • the solvent 104 may be water, carbonates, furan, oxane, ether, ketone, ester, amide, acetate, siloxane, or combinations thereof.
  • Some explicit examples of the salt 106 include A x Cl, A x SO 4 , A x NO 3 , A x PO 4 ,A x Br, A x I, A x AlO 2 , A x Ac(acetate), A x PF 6 , A x BF 6 , A x ClO 4 , A x AsF 6 , A x AlCl 4 , A x B 5 Cl 5 , A x CF 3 SO 3 , A x (CF 3 SO 2 ) 2 N, and A x (C 2 F 5 SO 2 ) 2 N, where ‘‘A’’ is an alkali or alkaline earth element.
  • the R alkene or alkane includes a substitution such as oxygen, silicon, fluorine, chlorine, phosphorus, aluminum, arsenic, selenium, bromine, or combinations thereof.
  • R is the alkene chain -CH 2 -CH 2 -CH 2 -
  • some part of R can be substituted with F to form -CHF-CH 2 -CH 2 -, with O to form -CH 2 -O-CH 2 -, or with Cl to form -CH 2 -CH 2 -CCl 2 -.
  • G and g are independently selected from an alkene or alkane group.
  • G is an alkene
  • g may be either an alkene or an alkane.
  • G is an alkane
  • g may be either an alkene or an alkane.
  • R may be the same as either G or g.
  • the percentage by weight (wt%) of additive 108 to solution 102 is in a range of 0.1 to 50 wt%.
  • Fig. 2 is a partial cross-sectional view of a TMCM electrode battery.
  • the battery 200 comprises a TMCM cathode 202 and an anode 204.
  • an ion-permeable barrier 206 may separate the cathode 202 from the anode 204.
  • An electrolyte as described above in the explanation of Fig. 1, comprises a solution 102 including a solvent 104 and either an alkali or alkaline earth metal salt 106.
  • the electrolyte also includes additives 108, comprising G-R-g:
  • G and g are independently selected from a group of materials including the element of nitrogen (N) sulfur (S), oxygen (O), or combinations of the above-recited elements; and,
  • R is an alkene or alkane group.
  • the solvent 104 may be water, carbonates, furan, oxane, ether, ketone, ester, amide, acetate, siloxane, or combinations thereof.
  • Some explicit examples of the salt 106 include A x Cl, A x SO 4 , A x NO 3 , A x PO 4 ,A x Br, A x I, A x AlO 2 , A x Ac(acetate), A x PF 6 , A x BF 6 , A x ClO 4 , A x AsF 6 , A x AlCl 4 , A x B 5 Cl 5 , A x CF 3 SO 3 , A x (CF 3 SO 2 ) 2 N, and A x (C 2 F 5 SO 2 ) 2 N, where ‘‘A’’ is an alkali or alkaline earth element.
  • the R alkene or alkane includes a substitution such as oxygen, silicon, fluorine, chlorine, phosphorus, aluminum, arsenic, selenium, bromine, or combinations thereof.
  • G and g are independently selected as alkanes or alkenes. As noted above, G and g may not be the same material, but R may be the same as either G or g.
  • the percentage by weight (wt%) of additive 108 to solution 102 is in a range of 0.1 to 50 wt%.
  • the TMCM cathode 202 is expressed by the formula B n M1 p M2 q (CN) r . fH 2 O;
  • B is a first group of metals that may, for example, be an alkali or alkaline earth metal
  • M1 and M2 are independently selected from a second group of transition metals
  • n is in a range of 0 to 2;
  • f is in a range of 0 to 20;
  • Some examples from the first group of metals include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al), magnesium (Mg), and combinations thereof.
  • M1 and M2 are each independently selected from the second group of metals that includes titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), niobium (Nb), ruthenium (Ru), tin (Sn), indium (In), cadmium (Cd), calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba).
  • M1 and M2 may, or may not be the same metal.
  • the anode 204 can be made from carbonaceous materials, alkali metals, alkaline earth metals, alloys including tin, alloys including lead, alloys including silicon, alloys including phosphorous, alloys including germanium, titanates including alkali metals, titanates including alkaline earth metals, or combinations thereof.
  • Fig. 3A depicts a fresh TMCM electrode immersed in an electrolyte containing additives.
  • Fig. 3B depicts additives interacting or coordinating with defects on the surface of TMCM electrode to stabilize its structure.
  • mobile ions 300 can ‘‘rock’’ back and forth between TMCM electrode 202, depicted as and the counter electrode (not shown).
  • Metal cyanide vacancies or transition metal defects 302 occur, and undercoordinated metal ions 306 appear in TMCM, especially near the surface, making the cathode unstable.
  • the B-ions In its charged state the B-ions are completely removed from the TMCM and its framework may collapse, starting from the surface, due to the lack of supporting B-ions.
  • undercoordinated metal ions can impede the charge transfer across the interface between the electrode and electrolyte because of charge repulsion between undercoordinated metal ions and B-ions.
  • an additive 108 is added into the electrolyte 100.
  • G and g represent groups containing nitorogen (N), and/or sulfur (S), and/or oxygen (O).
  • R is an alkene or alkane group that may be fluoridized.
  • G and g interact or coordinate with transition-metal ions near the cathode surface 304 to stabilize the structure of TMCM electrode 202.
  • the groups also can connect with the undercoordinated metal ions on the surface to reduce their repulsion to B-ions.
  • Fig. 3B depicts the surface modification of TMCM electrode 202 with additives 108 in the electrolyte 100.
  • Figs. 4A and 4B are an example of a Prussian White (PW, Na 2 Fe 2 (CN) 6 ) electrode where no electrolyte additive has been used, respectively showing capacity vs. cycles, and capacity vs. voltage.
  • PW Prussian White
  • CN CN
  • Figs. 4A and 4B are an example of a Prussian White (PW, Na 2 Fe 2 (CN) 6 ) electrode where no electrolyte additive has been used, respectively showing capacity vs. cycles, and capacity vs. voltage.
  • Figs. 5A and 5B are an example of the PW electrode where any electrolyte additive has been used, respectively showing capacity vs. cycles, and capacity vs. voltage.
  • ADN adiponitrile
  • the lone pair electrons in nitrogen interact with d-orbitals of Fe so that the ADN chains can fill up the defects/vacancies to stabilize the PW structure.
  • the ADN additive did not cause a significant difference in the PW electrode charge/discharge profiles and its initial capacity, but improved its cycling performance remarkably as shown.
  • Fig. 6 is a graph comparing the PW electrodes, with and without the ADN additive.
  • the PW electrode with ADN additive retained 92.6% of its initial capacity.
  • just 70.1% of initial capacity was retained in PW electrode without ADN.
  • ADN stabilized the structure of PW electrode and improved its cycle life.
  • Fig. 7 is a flowchart illustrating a method for self-repairing a TMCM battery electrode. Although the method is depicted as a sequence of numbered steps for clarity, the numbering does not necessarily dictate the order of the steps. It should be understood that some of these steps may be skipped, performed in parallel, or performed without the requirement of maintaining a strict order of sequence. Generally however, the method follows the numeric order of the depicted steps. The method starts at Step 700.
  • Step 702 provides a battery comprising a TMCM cathode, an anode, and an electrolyte.
  • the electrolyte includes a solution comprising a solvent, an alkali or alkaline earth salt, and an additive comprising G-R-g:
  • G and g are independently selected from a group of materials including the element of nitrogen (N) sulfur (S), oxygen (O), and combinations of the above-recited elements; and,
  • R is an alkene or alkane group.
  • an alkene is an unsaturated, aliphatic hydrocarbon with one or more carbon-carbon double bonds.
  • An alkane is a saturated hydrocarbon, consisting of only hydrogen and carbon atoms, with single bonds.
  • the percentage by weight of additive to solution is in the range of 0.1 to 50 wt%.
  • the battery provided in Step 702 is as described above in the explanation of Fig. 2, above.
  • Step 704 creates vacancies and defects in a surface of the TMCM cathode.
  • the battery is discharged by connecting an external load between the anode and cathode.
  • Step 706 fills the vacancies and defects in the surface of the TMCM cathode with the electrolyte additive.
  • solvents include water, carbonates, furan, oxane, ether, ketone, ester, amide, acetate, siloxane, and combinations thereof.
  • salts include A x Cl, A x SO 4 , A x NO 3 , A x PO 4 ,A x Br, A x I, A x AlO 2 , A x Ac(acetate), A x PF 6 , A x BF 6 , A x ClO 4 , A x AsF 6 , A x AlCl 4 , A x B 5 Cl 5 , A x CF 3 SO 3 , A x (CF 3 SO 2 ) 2 N, and A x (C 2 F 5 SO 2 ) 2 N, where ‘‘A’’ is either an alkali or alkaline earth elements.
  • the R alkene may include one of the following substitutions: oxygen, silicon, fluorine, chlorine, phosphorus, aluminum, arsenic, selenium, bromine, and combinations thereof.
  • G and g are independently either an alkene or alkane. Note: the examples listed above are not an exhaustive list of materials.
  • An electrolyte has been provided with an additive useful in the self-repair of TMCM battery electrodes. Examples of particular materials have been presented to illustrate the invention. However, the invention is not limited to merely these examples. Other variations and embodiments of the invention will occur to those skilled in the art.
  • SLA3352 Cyanometallate Cathode Battery and Method for Fabrication, invented by Yuhao Lu et al, Serial No. 14/174,171, filed February 6, 2014, attorney docket No. SLA3351; (11) SODIUM IRON(II)-HEXACYANOFERRATE(II) BATTERY ELECTRODE AND SYNTHESIS METHOD, invented by Yuhao Lu et al, Serial No. 14/067,038, filed October 30, 2013, attorney docket No. SLA3315; (12) TRANSITION Metal HexacyanoMETALLATE-CONDUCTIVE POLYMER COMPOSITE, invented by Sean Vail et al., Serial No.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un procédé pour l'autoréparation d'une électrode de batterie au cyanométallate d'un métal de transition (TMCM). La batterie est constituée d'une cathode en TMCM, d'une anode et d'un électrolyte comprenant une solution formée à partir d'un solvant et d'un sel d'un métal alcalin ou alcalino-terreux. L'électrolyte comprend un additif représenté par G-R-g : où G et g comprennent d'une manière indépendante des matériaux contenant de l'azote (N), du soufre (S), de l'oxygène (O) ou des combinaisons des éléments ci-dessus ; et où R est un groupe alcène ou alcane. En réponse à une charge et à une décharge de la batterie sur une pluralité de cycles, le procédé crée des trous dans une surface de la cathode en TMCM. Le procédé remplit alors les puits se trouvant dans la surface de la cathode en TMCM avec l'additif pour électrolyte. Un électrolyte et une batterie TMCM utilisant les additifs mentionnés ci-dessus sont aussi présentés.
PCT/JP2015/003261 2014-06-30 2015-06-29 Additifs pour électrolyte pour stabilisation d'électrodes en cyanométallate d'un métal de transition Ceased WO2016002194A1 (fr)

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CN201580035681.8A CN106688133A (zh) 2014-06-30 2015-06-29 用于使过渡金属氰合金属酸盐电极稳定的电解质添加剂

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US14/320,352 2014-06-30
US14/320,352 US9620815B2 (en) 2012-03-28 2014-06-30 Electrolyte additives for transition metal cyanometallate electrode stabilization

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US10122049B2 (en) 2014-02-06 2018-11-06 Gelion Technologies Pty Ltd Gelated ionic liquid film-coated surfaces and uses thereof
EP4165710A1 (fr) 2020-06-11 2023-04-19 Natron Energy, Inc. Additifs d'électrolyte destinés à une cellule électrochimique

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CN107369846B (zh) * 2017-07-14 2020-10-27 北京理工大学 电极片及其制备方法和铝离子电池
CN113078416B (zh) * 2021-03-22 2022-03-15 电子科技大学 一种纳米花状CoIn2S4颗粒/石墨烯复合修饰的隔膜
CN114709478A (zh) * 2022-03-30 2022-07-05 厦门大学 含Se=P双键有机化合物在制备二次电池电解液中的应用

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JP2008108586A (ja) * 2006-10-26 2008-05-08 Hitachi Maxell Ltd 非水二次電池
WO2013157660A1 (fr) * 2012-04-17 2013-10-24 Sharp Kabushiki Kaisha Batterie aux ions de métaux alcalins et alcalinoterreux comprenant une cathode héxacyanométallate et une anode non métallique

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10122049B2 (en) 2014-02-06 2018-11-06 Gelion Technologies Pty Ltd Gelated ionic liquid film-coated surfaces and uses thereof
EP4165710A1 (fr) 2020-06-11 2023-04-19 Natron Energy, Inc. Additifs d'électrolyte destinés à une cellule électrochimique
EP4165710A4 (fr) * 2020-06-11 2025-04-02 Natron Energy, Inc. Additifs d'électrolyte destinés à une cellule électrochimique

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