• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    rechargeable alkali and alkaline earth metal electrodes having controlled dendritic growth, and process for their production and use. the present invention relates to a device for extending the useful life of a battery, including an electrode having a metallic part, wherein the metallic part is selected from the group including lithium, calcium, magnesium, sodium, potassium and combinations thereof, an electrolyte permeable membrane, and a metallic dendrite nucleation material disposed between the electrode and the membrane. at least one dendrite, extending from the electrode towards the electrolyte-permeable membrane, combines with at least one dendrite, extending from the dendrite nucleation material.
    公开号:BR112013029242B1
    申请号:R112013029242-3
    申请日:2012-05-17
    公开日:2021-06-22
    发明作者:Jian Xie
    申请人:Indiana University Research And Technology Corporation；
    IPC主号:
    专利说明:

    CROSS REFERENCE TO RELATED PATENT APPLICATIONS
    [0001] This utility model patent application claims priority to co-pending US provisional patent application Serial No. 61/486,949, filed May 17, 2011, co-pending US provisional patent application Serial No. 61 /498,192, filed June 17, 2011, and co-pending US provisional patent application Serial No. 61/565,101, filed November 30, 2011, all of which are incorporated by reference into this specification. BACKGROUND
    [0002] The use of lithium metal as an anode to establish a rechargeable lithium cell or battery system, with the highest anode specific capacity, has been highly desired. However, the growth of lithium metal dendrites poses serious technical barriers to developing this battery. Recently, modified versions of the lithium metal battery, such as the lithium ion battery, have been introduced with some success. However, current modified versions have limitations and inefficiencies that would not appear with a cell that uses lithium metal as an anode.
    [0003] Typically, a lithium metal cell includes an anode and a cathode, separated by an electrically insulating barrier or "separator" and operatively linked by an electrolyte solution. During the charging process, the positively charged lithium ions move from the cathode, through the permeable separator, to the anode, and are reduced to metallic lithium. During discharge, metallic lithium is oxidized to positively charged lithium ions, which move from the anode, through the separator, and to the cathode, while electrons move by an external charge from the anode to the cathode, generating current and providing energy for the charge. During repeated charging and discharging, lithium dendrites begin to grow on the anode surface. Lithium dendritic deposits, sometimes called granular lithium, eventually break through the separator and strike the cathode, causing an internal short and rendering the cell inoperable. The formation of lithium dendrites is inherently unavoidable during the charging and discharging processes of metallic lithium cells. Thus, there remains a need for a lithium electrode cell system, which does not suffer from the effects of dendrite growth, while simultaneously maintaining the cycling capacity, ionic conductivity, voltage and specific capacity of the cells. The present new technology addresses these needs. BRIEF DESCRIPTION OF THE DRAWINGS
    [0004] FIG. 1 is a schematic view of a lithium ion cell, in accordance with a first embodiment of the present new technology.
    [0005] FIG. 2A is a perspective view of the separator of FIG. 1.
    [0006] FIG. 2B is a detailed view of the surface of the separator of FIG. two.
    [0007] FIG. 3A is a first perspective view of the composite electrode of FIG. 1.
    [0008] FIG. 3B is a second perspective view of the composite electrode of FIG. 1.
    [0009] FIG. 3C is a third perspective view of the composite electrode of FIG. 1.
    [00010] FIG. 3D is a fourth perspective view of a composite electrode of FIG. 1.
    [00011] FIG. 4 is a perspective view of a second embodiment of coin cell implementation of the present new technology.
    [00012] FIG. 5 is an enlarged elevation view of a dendrite growth from an electrode surface of FIG. 1.
    [00013] FIG. 6 is a detailed view of the surface of the separator of FIG. 1, as partially coated with FNC.
    [00014] FIG. 7 is a process diagram of a third embodiment of the present new technology, showing a process for forming dendrite nucleating material.
    [00015] FIG. 8 is a process diagram of a fourth embodiment of the present new technology, showing a metallic dendrite growth control process.
    [00016] FIG. 9 is a process diagram of a fifth embodiment of the present new technology, showing a process of extending the life of a cell.
    [00017] FIG. 10 is a process diagram of a sixth embodiment of the present new technology, showing a process for producing a FNC coated separator. DETAILED DESCRIPTION
    [00018] For the purposes of promoting and understanding the principles of the new technology and presenting the best operating mode currently understood, reference will then be made to the modalities illustrated in the drawings, and specific language will be used to describe them. It should, however, be understood that no limitation on the scope of the new technology is thereby intended, with these changes and other modifications to the illustrated new technology and these other applications of the new technology principles, as illustrated in this descriptive report, being considered as a normal occurrence to those versed in the technique.
    [00019] As shown in FIGURES 1 - 10, the present new technology relates to a rechargeable lithium metal electrochemical storage cell 10, having lithium metal electrodes 20. Referring to FIG. 1, a rechargeable lithium electrode cell 10 is shown with a lithium metal cathode part 12 and a lithium metal anode part 14. Separator 50 is positioned between anode 14 and cathode 12. Separator 50 is typically coated with a layer 80 of 40 nanometer functionalized carbon particles. Separator 50 includes a side facing the anode 53 and a side facing the cathode 52, and is typically coated with a thin or very thin film 80 of the nanometer particles of functionalized carbon (FNC) 40, most typically of a thickness of about 0.1 µm, and typically oriented toward the surface 70 of the lithium metal electrode 20. The span 26 is filled with an electrolyte 25, positioned between the lithium metal electrode 30 and the separator coated with FNC 60. Functionalized carbon nanometer particles 40 typically have Li+ ions immobilized on surface 65 of layer 80 of carbon nanometer particles 40. The FNC film 80 is electrically connected to the lithium metal electrode 20. When the lithium metal electrode 20 is charged, the lithium dendrites 11 extend from the surface 70 of the lithium metal electrode 20 towards the FNC coated separator 60. Simultaneously, the dendrites 55 extends from the surface 65 of the FNC 80 film towards the surface 70 of the lithium metal electrode 20. The dendrites 55 grow in the direction along plane 94 of the lithium metal electrode 20 and the FNC coated separator 60.
    [00020] With reference to FIG. 5, the growth of dendrites 11, 55 is triggered by the potential difference (ΔE) between the tip (Et) 59 and the base (Eb) of the respective dendrites 11, 55. With cycling, the dendrites 11, 55 continue to extend each other; eventually, the dendrites 11, 55 touch, and the potential difference (ΔE) 11, 55 is approximately zero, because the FNC film 80 and the lithium metal electrode 20 have the same potential. Consequently, the growth of dendrites 11, 55 is slowed or stopped along the direction by plane 94. In subsequent cycles, dendrites 11, 55 may grow in a direction perpendicular to the large axis of the respective dendrite 11, 55 and parallel to the plane of the lithium metal electrode 20, also referred to as the in-plane direction 84, which prevents dendrites 11, 55 from piercing permeable or selectively permeable membrane 50, as shown in FIGURES 3A - 3D. Eventually, a lithium secondary surface 70 can form from the intersection of lithium dendrites 11, 55. In this way, a lithium metal composite electrode 20 is formed, in which a lithium electrode 20 is constituted with the thin layer of 80 carbon.
    [00021] Although lithium is typically discussed specifically as the electrode metal, the storage cell 10 may alternatively include other alkali and alkaline earth metal elements and their combinations as the electrode materials.
    [00022] Two types of exemplary cell configurations to explore the lithium metal electrode/dendrite system include a symmetric cell 400, in which a lithium metal electrode 420 is used as both anode 414 and cathode 412 having the configuration of Li/polymer/Li (anode/electrolyte/cathode = A/E/C), allowing a study of lithium dendrite mechanism or Li/polymer battery systems; and an asymmetric cell 500 in which the metallic lithium is anode 514, and a different material is selected for cathode 512, such as Li/polymeric electrolyte/V2O5, Li/liquid electrolyte/graphite, Li/polymeric electrolyte/graphite and Li /polymeric electrolyte/FePO4. The symmetric cell 400 provides a better medium for the growth of lithium metal dendrites, and can speed up the cycling assay, while the asymmetric cell 500 comes closer to field applications.
    [00023] The growth of dendrites as shown in FIG. 5, is fundamentally unavoidable because the metallurgical characteristics of lithium metal surfaces result in surface imperfections of lithium metal electrodes after application of mechanical stress or deposition/extraction cycles. Although art-known configurations focus only on stopping the growth of dendrites 11, the new cell design 10 focuses on controlling the direction of growth of lithium metal dendrites 11, 55.
    [00024] As described in FIG. 9, an 800 implementation of the new electrode 20 may have a carbon coated layer of functionalized carbon nanometer particles (FNC) 80 in a separator 50, which is positioned 801 in an electrolyte 25 and grows lithium dendrites 803 11, 55 simultaneously from the surface 51 of the lithium metal electrode 20 and the surface of the separator coated with FNC 60. An electrolyte 25 is placed 802 in span 26, between electrode 20 and the separator coated with FNC 60. Dendrites 11, 55 grow 803 after repeated charges and discharges 804 from cell 10. Dendrites 11, 55 are in contact with each other 805, and when contact occurs, dendrites 11, 55 stop extending in the direction of plane 94, due to the resulting zero potential difference. of the contact. Control of the growth direction of dendrites 800 takes place by 805 contact between the separator dendrites coated with FNC 55 and the dendrites of electrode 11. After multiple combinations of dendrites 11, 55, it results in 806 formation of a lithium-de secondary lithium 70.
    [00025] The establishment of a zero potential difference gives the rechargeable lithium metal electrode 20 a high specific capacity, a high cycling capacity and a high safety. Consequently, the rechargeable lithium metal electrode system 10 can be implemented in many types of lithium batteries, including Li - polymer, Li - air and Li - metal oxide cell and battery systems, as well as any other lithium oxide systems. batteries or cells in which lithium metal anodes 14 are used, and generate benefits for electronic components, electric vehicles and hybrid electric vehicles, large-scale energy storage and the like.
    [00026] Typically, a challenge for the development of a high specific capacity rechargeable lithium metal electrode 20 for different lithium batteries (ie Li - polymer, Li - air and Li ion, etc.) has been stop the growth of dendrites from electrode 11 during cycling 803. The lithium metal electrode 20 has an inherent metallurgical tendency to form dendrites 11, and the growth of dendrites 11 is driven by the potential difference between the base 57 and the dendrite tip 59. Thus, the growth of dendrites of electrode 11 is inevitable. However, the present system 800 incorporates, rather than avoids, the dendrite growth mechanism.
    [00027] In one embodiment, a rechargeable lithium metal electrode 220 is used in other lithium battery systems, such as Li - polymer and Li - air, and can be produced by coating layers of FNC 280 on membranes. 200 polymeric electrolytes, which are used as the 225 electrolyte in both Li - polymer and Li - air batteries. These 225 FNC-coated polymeric electrolytes are typically incorporated as the intermediate layer 280 and mounted in a soft-encased Li-air cell 285. These 260 polymeric electrolyte membranes may include those of poly(ethylene oxide) (PEO), poly (vinylidene fluoride) (PVdF), polyacrylonitrile (PAN) and other polymeric electrolytes, which are widely used in both Li - polymer and Li - air batteries.
    [00028] Additionally, many production modes of the FNC 60 coated separator are available. The FNC layer 80 plays a role in the new lithium metal electrode 20 in that the immobilized Li+ ions 30 in the FNC layer 80 serve as "seeds" for the formation of lithium metal dendrites 55 in the FNC layer 80. FNC layer 80 is typically porous, allowing FNC aggregates to be bonded together 605 by binder network 604 to form a rigid structure 606 to maintain 607 the integrity of layer 80. Layer 80 is typically very thin with four properties main: 1) good pore structure to facilitate the passage of Li+ ions through it; 2) high electrical conductivity to reduce internal impedance; 3) high coverage of Li+ 30 ions on the 65 nanometer carbon surface for easy formation of 55-metal lithium dendrites; and 4) good adhesion to a polymeric separator 50 or a polymeric electrolyte membrane. All of these properties are similar to those for the catalyst layer in the fuel cell (ie, a porous layer for gas and water diffusion, electrical conductivity needed for gaseous reactions, SO3 coating for proton conduction, and good adhesion of the catalyst on the polymeric electrolyte membrane for durability). The thinner the FNC 80 layer, the smaller the specific capacity loss of the lithium metal electrode 20.
    [00029] The morphology of the FNC layer 80 depends on how the layer is manufactured 601. These application techniques 609 of layer 80 include: (1) spraying; (2) machine blade coating; (3) hand painting with a brush; and the like. Carbons can be selected from sources including carbon blacks, nanometric graphites, graphenes and the like. It was found that the greater the degree of graphitization, the greater the chemical stability. The 40 nanometer carbon particles can be made from carbon black, which is cheap but is an amorphous structure rather than a graphitic structure. Graphene can also be used and has unique properties such as high electronic conductivity, high modulus and high surface area.
    [00030] The morphology of the FNC 80 layer is also influenced by the paint formulation. To produce a thin layer of carbon, the first step is to mix 600 carbon source with solvents to produce an evenly dispersed suspension 603. To form a well dispersed carbon ink, the type of solvent is carefully selected based on polarity ( that is, the dielectric constant) and its hydrophobicity, to be equal to that of carbon aggregates and binders. This 602 mixture is also called "ink formulation". The type of carbons and solvents in a paint will affect the morphology of the FNC 80 thin layer. The type of binder 33 also affects the adhesion of the layer of carbon 80 in the separator 50. Typically, the binder 33 has a chemical structure similar to the membrane of the separator/electrolyte 50 so that it can be fused together 605 by heat pressing, or other technique, to form a well-bonded interface 62 between the carbon layer 80 and the membrane of the separator/electrolyte 50.
    [00031] The immobilized Li+ ions 30 on the surface of nanosized carbon particles 40 serve as the "seeds" 31 for the formation of lithium dendrites 55 in the separator coated with FNC 60. The immobilization of the Li+ ions 30 is conducted by forming 900 of a dendrite 61 nucleation material, such as by reaction with diazonium or a similar means 902 in a suitable carbon 50 separator 901, to chemically affix an SO3H 902 group to the carbon 65 surface, allowing the separator to carbon 50 becomes functionalized 903. Then, the trapped SO3H is exchanged 906 for Li+ ions 30, to immobilize the Li+ ions 30 on the surface 65. In this way, a dendrite 61 nucleation material is formed 907. The dendrite nucleation material 907 dendrite 61 is typically carbonaceous, but can also be a metallic substrate, such as Li, Na, K, Al, Ni, Ti, Cu, Ag, Au and combinations thereof. The nucleation material 61 may also be a functionalized metallic substrate, such as a self-assembled monolayer structure, comprised of Au with a thiol-terminated organic molecule, which contains at least one functional group, such as SO3-M+, COO-M+ and NR3 +X-, an electrically conductive organic polymer, such as polyacetylene, poly(phenylene-vinylidene), polypyrrole, polythiophene, polyaniline and poly(phenylene sulfide), or an electrically conductive organic polymer, in which the functional groups are chemically bonded to the polymer. Such materials 61 can be deposited using conventional physical deposition techniques, such as mechanical layering, or physical vapor deposition techniques, such as cathodic disintegration, or the like.
    [00032] The new technology allows 903 fixation of different functional groups on the surface of carbon 65, such as by diazonium reaction and the like. In this reaction, the functional group Y is attached 903 to the surface of carbon 65 by introducing 904 a diazonium salt XN2C6H4-Y (where Y = sulfonate, SO3-M+, carboxylate, COO-M+; and tertiary amine, NR3+X -; etc.). The fixation of different chemical groups not only provides a platform for immobilizing Li+ 30 ions on the surface of FNC 65, but also alters the surface energy of the carbon particles, which can be used as a tool to adjust the surface hydrophobicity of the film. of carbon 80, and is useful for formulating ink 603.
    [00033] The 609 adhesion of the FNC layer in a separator/polymeric electrolyte 50 influences the cyclic life of the new lithium metal electrode 20. A good interface 62, between the FNC layer 80 and the separator membrane/ electrolyte 50, is typically formed 608. This essentially depends on the network of binder 33 in the FNC layer 80 and the techniques for forming the interface 62. This catalyst layer can withstand several thousand hours of long-term durability testing due to , in part, to binder 33, which holds 607 the FNC layer 80 bonded to the separator/electrolyte membrane 50. A TEM observation of this catalyst/membrane interface 62 will show little or no delamination after approximately 2000 hours of testing. durability. Hot pressing is one of the techniques for production, and the parameters of the hot pressing technique (ie, temperature, pressure and time) provide for systematic process control.
    [00034] The morphology (ie surface area, pore structure and geometry) of the FNC layer 80 in membrane 50 has a significant impact on the performance of the new metallic electrode 20. The porosimetry 81 of the FNC layer 80 (ie, pore size, pore size distribution, and pore volume) is a factor in controlling the direction of dendritic growth 700, because it influences the 705 presence of metallic cations 30 on the FNC membrane surface 65 and the addition 703 of the dendrite nucleation material 61. The pore structure typically allows the metal ions 30 to pass directly evenly during cycling 704, but not to form dendrites within the pores, which would block the diffusion of the metal ions 30 Thus, determination 701 and production 702 of a suitable FNC layer 80, with porosimetry 81, is useful in allowing the presence 706 of dendrites 11, 55 and the eventual formation 707 of a secondary metallic layer 70. side, the FNC layer 80 must adhere to a separating membrane/electrolyte 50 and the diffusion barrier (if any) from the formed interface 62 must be minimized.
    [00035] Typically, the specific capacity of the rechargeable metal electrode 20 can be affected by varying the thickness 89 of the FNC 80 film against the thickness 29 of the lithium metal electrode 20. The examples presented in this descriptive report refer to the new technology and various modalities, and are not intended to limit the scope of the present new technology to those modes and modalities discussed in this descriptive report. Example 1:
    [00036] The effect of the different carbon-coated layers on the specific capacity of the lithium metal composite electrode 20 was calculated approximately and is shown in Table 1. For example, for the carbon-coated layer 80 with a thickness of 0.1 μm , the corresponding specific capacity loss of the lithium metal electrode 20 is only 0.026%. Even for 80.4 µm thick FNC film, the corresponding loss of specific capacity is only 0.53%. Thus, the effects of the carbon coated layer 80 on the specific capacity of the lithium metal electrode 20 are negligible. The thin 80 carbon coated layer maintains the advantage of the high specific capacity of lithium metal electrodes. Table 1

    [00037] Effect of carbon film thickness on the specific capacity of the lithium metal electrode.
    [00038] Therefore, carbon proved to be very stable over a wide window of potentials. The composite lithium electrode having a very thin carbon film is very stable. Carbon black can be used in many battery systems (ie Zn/MnO2), in particular lithium ion batteries (such as the anode) and Li-SOCl2 batteries (such as the carbon cathode).
    [00039] With reference to FIG. 4, the lithium metal anode 14 was established together with a separator 350 (thickness = 25 μm), coated with a thin layer of 80 nanometric carbon of 340 functionalized carbon nanoparticles (δ = 3.2 μm) and a cathode of LiPFeO4 312 in a 300 coin cell configuration using 1.2 M LiPF6 electrolyte in ethylene carbonate/ethyl methyl carbonate (EC:EMC = 3.7). A coin cell using the same components, but without the 380 nanometer carbon coating layer, was used as a baseline for comparison. A concern for the use of this carbon 380 coating layer is whether the addition of the FNC layer 380 to the separator 350 will result in greater internal impedance of the carbon layer 380, blocking the pores of the separator 350, thereby preventing diffusion of the 330 Li+ ions by them and consequently reducing the energy performance of the cell 300. However, it is clear that the coating of the carbon layer 380 in the separator 350 did not cause an increase in the internal impedance of the cell 300, but in instead, it resulted in a slight reduction in impedance. The Li/FNC 300 cell has a slightly higher discharge voltage than the baseline Li cell. Even after five hundred cycles, the same trend was observed. Noise was observed for the baseline cell, which was attributed to the formation of 355 dendrites. In addition, the same phenomenon of internal impedance reduction was observed during the charging process.
    [00040] Cell 300 was not balanced for capacity, and cell capacitor 300 was limited by LiPFeO4 cathode 312; a much larger capacity of the cell 300 is expected if a suitable high energy density cathode is used (such as a V2O5 airgel or an air cathode). The lithium metal electrode 314 using a layer of FNC 380 showed an excellent cycling capability, approximately 84% of the capacity after 500 cycles. The estimated capacity decay rate of the new 300 lithium metal electrode cell, after the first 45 cycles, is only 0.026%/cycle. Based on this decay rate, the cycle time of that cell can typically reach at least 500, more typically at least 725 cycles, and even more typically at least 1,000 cycles, with a capacity of 80% (death battery setting in electric vehicle applications - EV). This decay rate (0.026%/cycle) of the new lithium metal electrode 320, in the coin cell 300, can be caused by the degradation of the LiFe-PO4 312 cathode, because the coin type cells 300 are sealed at atmospheric pressure This can allow moisture to be introduced into the 300 cell. Moisture reacts with LiPF6 to produce HF, which can react with LiFePO4, causing degradation. Therefore, the true decay rate of the new lithium metal electrode 320 should be much lower than 0.026%/cycle if the coin cell 300 is sealed, such as inside an argon-filled glove box. Example 2:
    [00041] With reference to FIG. 6, a separator coated with FNC 60 was examined by SEM analysis after repeated cycling. Lithium metal 55 dendrites were observed on the surface 65 of the FNC 60 coated separator, facing the surface of the lithium metal electrode 20. Furthermore, the lithium 55 dendrites formed a unitary layer rather than an aggregation as loosely arranged dendrites . The thickness 89 of the FNC layer 80 was measured to be about 3 µm, while the lithium dendrite layer 70 had a thickness around 20 µm. Referring to FIG. 6, and to further illustrate the function of the FNC layer 80 to induce the formation of lithium metal dendrites 55, the separator 50 was coated with a layer of FNC 80 on half the surface area, while the other half was not. coated. No dendrites 55 were formed in the uncoated region of separator 50. No dendrites were found on the opposite side of the separator coated with FNC 50. Some large particles (50 µm or more) were observed under separator 50, these large particles also originated from the SEM conductive slurry used to adhere the separator sample to the SEM aluminum disc.
    [00042] In another modality, the layer 80 formed on the electrochemical separator 50, to provide dendritic growth towards the metallic anode 14, is a thin metallic layer 80. The dendrites 55 growing from the separator 50 come in contact with the dendrites - dendrites 11 growing from metallic anode 14, promoting a short and thereby preventing dendrites 11, growing from anode 14 towards separator 50, from reaching and piercing separator 50. Anode 14 is typically lithium, but may be also sodium or similar. Metal layer 80 in separator 50 is typically lithium, but may be sodium or other electrically conductive metal, electrically conductive polymer, an organometallic matrix, functionalized electrically conductive polymer, or the like. More typically, layer 80 is a non-reactive metal, such as nickel. Metal layer 80 in separator 50 is typically formed thin enough so that its electrical resistivity is high, typically high enough that layer 80 is not easily degraded electrically or otherwise. Optionally, thin metallic layer 80 can be functionalized after depositing in separator 50.
    [00043] Although the new technology has been illustrated and described in detail in the drawings and description above, it should be considered as illustrative and not restrictive. It should be understood that the modalities were shown and described in the descriptive report presented above satisfying their best way and satisfying the requirements. It should be understood that a person skilled in the art will easily make an infinite number of insubstantial variations and modifications to the modalities described above, and that it would be impractical to attempt to describe all such modalities variations in this specification. Consequently, it must be understood that all variations and modifications, which fit the spirit of the new technology, are intended to be protected.
    权利要求:
    Claims (14)
    [0001]
    1. A lithium metal battery cell comprising: an electrolyte medium (25); a cathode positioned in the electrolyte medium; a lithium-containing anode (20) positioned in the middle of the electrolyte (25) and spaced from the cathode; a separator (60) comprising an electrically insulating barrier member (50,350) having an anode-facing side (53) and a cathode-facing side (52) disposed between the lithium-containing anode and the cathode, characterized in that the span (26) is filled with the electrolyte medium (25) and positioned between lithium-containing anode (20) and the separator (60), and an electrically conductive porous layer (80, 380) of a plurality of functionalized carbon nanoparticles - Lithium shells (40) operationally connected and adhered to the side facing the anode (53) of electrically insulating barrier, separator member (60), where the separator (60) is electrically insulating and electrolytically permeable.
    [0002]
    2. Battery cell according to claim 1, characterized in that the various dendrites (11) extend from the lithium-containing anode towards the separator, and the various dendrites (55) extend from the side facing the separator anode towards the anode containing lithium.
    [0003]
    3. Battery cell according to claim 2, characterized in that the various dendrites (11, 55) combine in the electrolyte medium and have a potential difference of approximately zero.
    [0004]
    4. Battery cell according to claim 3, characterized in that the various dendrites define a secondary metallic lithium layer.
    [0005]
    5. Battery cell according to claim 1, characterized in that the battery cell is a coin-type cell (300).
    [0006]
    6. Battery cell according to claim 1, characterized in that the battery cell is rechargeable.
    [0007]
    7. Battery cell according to claim 1, characterized in that the battery cell is symmetrical.
    [0008]
    8. Battery cell according to claim 1, characterized in that the functionalized nanocarbon particles are selected from the group including carbon black, graphene, graphite, nanometric graphite, amorphous carbon and combinations thereof.
    [0009]
    9. Battery cell according to claim 1, characterized in that the lithium cations ionically associate with a functional group selected from the group including sulfonate, carboxylate, tertiary amine, diazonium salt and combinations thereof.
    [0010]
    10. Battery cell according to claim 1 characterized by the fact that the electrically insulating barrier member is permeable to an organic electrolyte containing metal salts.
    [0011]
    11. Battery cell according to claim 1, characterized in that the metal is selected from the group including lithium, sodium, potassium, calcium, magnesium and combinations thereof.
    [0012]
    12. Battery cell according to claim 1, characterized in that it additionally comprises a bonded interface (62) between the layer (80, 380) of functionalized nanocarbon particles and the electrically insulating barrier member (50 , 350).
    [0013]
    13. Battery cell according to claim 1, characterized in that the layer (80,380) of functionalized nanocarbon particles (40, 340) is a film (80) of functionalized nanocarbon particles ( 40).
    [0014]
    14. Battery cell according to claim 13, characterized by the fact that the film (80) is electrically connected to a metallic lithium anode (14).
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    同族专利:
    公开号 | 公开日
    AU2017216465B2|2019-11-07|
    WO2012158924A3|2013-03-14|
    BR112013029242A2|2017-03-01|
    CN106252566A|2016-12-21|
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    JP6514290B2|2019-05-15|
    CN106252566B|2019-12-31|
    AU2012255242B2|2017-08-03|
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    EP3367467B1|2020-03-04|
    EP3367467A1|2018-08-29|
    SG10201405466RA|2014-10-30|
    CA2836466C|2019-07-23|
    CN103703587B|2016-09-07|
    RU2601548C2|2016-11-10|
    CA2836466A1|2012-11-22|
    JP2018029065A|2018-02-22|
    KR101970840B1|2019-08-13|
    CO6821922A2|2013-12-31|
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    US9590236B2|2017-03-07|
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    CN103703587A|2014-04-02|
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    JP2014517473A|2014-07-17|
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    法律状态:
    2018-04-24| B25G| Requested change of headquarter approved|Owner name: INDIANA UNIVERSITY RESEARCH AND TECHNOLOGY CORPORA |
    2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-06-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-04-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/05/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161486946P| true| 2011-05-17|2011-05-17|
    US61/486,946|2011-05-17|
    US201161498192P| true| 2011-06-17|2011-06-17|
    US61/498,192|2011-06-17|
    US201161565101P| true| 2011-11-30|2011-11-30|
    US61/565,101|2011-11-30|
    PCT/US2012/038360|WO2012158924A2|2011-05-17|2012-05-17|Rechargeable alkaline metal and alkaline earth electrodes having controlled dendritic growth and methods for making and using the same|
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