JP2017022096A - Electrochemical cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochemical cell such as Lithium and air cells with improving charge/discharge cycle characteristics.SOLUTION: An electrochemical cell includes a negative electrode 102 containing the form of lithium, a positive electrode 104 containing an electron conduction matrix 112 at a predetermined interval between itself and the negative electrode, a separator 106 placed between the negative electrode and the positive electrode, an electrolyte 114 containing salt and a charging redox pair located inside the positive electrode and is characterized by transport of electrons from a discharge product located at the positive electrode to the electron conduction matrix by the charging redox pair in a charge cycle.SELECTED DRAWING: Figure 4

Description

  [0001] The present invention relates to batteries, and more particularly to lithium (Li) based batteries.

  [0002] A typical Li ion cell includes a negative electrode or anode, a positive electrode or cathode, and a separator region between the negative and positive electrodes. One or both of the electrodes includes an active material that reacts reversibly with lithium. In some cases, the negative electrode can include lithium metal that can be reversibly electrochemically dissolved and deposited. The separator and the positive electrode include an electrolyte containing a lithium salt.

  [0003] Charging a Li-ion cell generally involves the generation of electrons at the positive electrode and the consumption of an equal amount of electrons at the negative electrode as the electrons are transported through an external circuit. In an ideal charging of the cell, these electrons are generated at the positive electrode because there is desorption due to oxidation of lithium ions from the active material of the positive electrode, and electrons are present at the reduction of lithium ions to the active material of the negative electrode Therefore, it is consumed at the negative electrode. During the discharge, the opposite reaction occurs.

  [0004] Li ion cells using Li metal anodes have higher specific energy (in Wh / kg) and energy density (in Wh / L) compared to batteries using conventional carbonaceous negative electrodes. obtain. With this high specific energy and energy density, incorporating a rechargeable Li-ion cell with a Li metal anode into the energy storage system is an attractive option for a wide range of applications, including portable electronics and electric and hybrid electric vehicles. Become.

[0005] Lithium interlayer oxides are commonly used in the positive electrodes of conventional lithium ion cells. Lithium interlayer oxides (eg LiCoO ₂ , LiNi _0.8 Co _0.15 Al _0.05 O ₂ , Li _1.1 Ni _0.3 Co _0.3 Mn _0.3 O ₂ ) are usually (lithiated) Limited to a theoretical capacity of about 280 mAh / g (based on the mass of the oxide) and a practical capacity of 180 to 250 mAh / g, this value is considerably lower compared to the specific capacity of lithium metal (3863 mAh / g) .

  [0006] Further, the low realized capacity of conventional Li ion cells reduces the effectiveness of incorporating Li ion cells into vehicle systems. Specifically, the goal for electric vehicles is to reach a cruising range comparable to that of modern vehicles (> 482.8 km (300 miles)). Needless to say, the size of the battery can be increased to increase capacity. However, the practical size of a battery on a vehicle is limited by the associated weight of the battery. As a result, the US Department of Energy (DOE) has set a long-term target for a maximum weight of electric vehicle battery packs of 200 kg (this value includes the storage container) in USABC Goals for Advanced Batteries for EVs. Achieving the required capacity requires a specific energy exceeding 600 Wh / kg, considering the DOE target.

[0007] Various materials are known to provide a higher theoretical capacity guarantee for Li-based cells. For example, a high theoretical specific capacity of 1168 mAh / g (based on the mass of the lithiated material) is shared by Li ₂ S and Li ₂ O ₂ and these can be used as cathode materials. Other high capacity materials include Amatocci, G. et al. G. And N.A. Pereira, "Fluoride based electrode materials for advanced energy storage devices", Journal
of Fluorine Chemistry, 2007.128 (4) , as reported by 243-262 _pages, there is BiF 3 (303mAh / g, lithiated) and _FeF 3 _(712mAh / g, lithiated). Unfortunately, all of these materials react with lithium at lower voltages compared to conventional oxide positive electrodes. Nevertheless, the theoretical specific energy is still very high (> 800 Wh / kg compared to a maximum of about 500 Wh / kg for a cell using a lithium negative electrode and a conventional oxide positive electrode).

[0008] One Li-based cell with the potential to provide a driving range in excess of 482.8 km (300 miles) incorporates a lithium metal negative electrode and a positive electrode that reacts with ambient oxygen. The weight of this type of system is reduced because the positive electrode active material is not carried on the vehicle. This practical embodiment of the lithium / air cell can achieve a practical specific energy of 600 Wh / kg because the theoretical specific energy is 11,430 Wh / kg for Li metal and Li ₂ It is because it is 3,460 Wh / kg with respect to O ₂ .

[0009] During discharge of a lithium / air cell, Li metal dissolves from the negative electrode, while at the positive electrode, lithium ions (Li ⁺ ions) in the electrolyte react with oxygen and electrons to form a solid discharge product; The product is ideally lithium peroxide (Li ₂ O ₂ ) or lithium oxide (Li ₂ O), the Li ₂ O ₂ or Li ₂ O covering the conductive matrix of the positive electrode, and It is possible to fill the pores of the electrode. In an electrolyte using a carbonate solvent, the discharge product can include Li ₂ CO ₃ , Li alkoxide, and Li alkyl carbonate. In non-carbonate solvents such as CH ₃ CN and dimethyl ether, the discharge product is unlikely to react with the solvent. The pure crystalline forms of Li ₂ O ₂ and Li ₂ O are electrically insulative, so that electronic conduction through these materials is the vacancies, granules, or dopants obtained by appropriate electrode constructions, Or it will need to be accompanied by a short conduction path.

  [0010] Abraham and Jiang have published one of the earliest papers on "lithium / air" systems. Abraham, K .; M.M. And Z. See Jiang, “A polymer electrical-based rechargeable lithium / oxygen battery”, Journal of the Electrochemical Society, 1996.143 (1), pages 1-5. Abraham and Jiang use a positive electrode with an organic electrolyte and a conductive carbon matrix that includes a catalyst to aid the reduction and oxidation reactions. Previous lithium / air systems using aqueous electrolytes are also considered, but without the protection of the Li metal anode, rapid hydrogen evolution occurs. Zheng, J. et al. Et al., “Theoretic Energy Density of Li-Air Batteries”, Journal of the Electronic Society, 2008.155, page A432.

[0011] An electrochemical cell 10 is illustrated in FIG. The cell 10 includes a negative electrode 12, a positive electrode 14, a porous separator 16, and a current collector 18. The negative electrode 12 is usually metallic lithium. The positive electrode 14 includes carbon particles, such as particles 20, which are optionally coated with a catalytic material (such as Au or Pt) and suspended within a porous conductive matrix 22. An electrolyte solution 24 containing a salt such as LiPF ₆ dissolved in an organic solvent such as dimethyl ether or CH ₃ CN permeates both the porous separator 16 and the positive electrode 14. LiPF ₆ provides an electrolyte with sufficient conductivity that reduces the internal electrical resistance of the cell 10 and enables high power.

The positive electrode 12 is surrounded by a barrier 26. The barrier 26 in FIG. 1 is formed of an aluminum mesh that is configured to allow oxygen from an external source 28 to enter the cathode 14. The wettability of the positive electrode 14 prevents the electrolyte 24 from leaking out of the positive electrode 14. While the cell 10 is discharged, oxygen from the external source 28 enters the positive electrode 14 through the barrier 26, and when the cell 10 is charged, oxygen flows out of the positive electrode 14 through the barrier 26. During operation, when the cell 10 discharges, oxygen and lithium ions combine to form a discharge product such as Li ₂ O ₂ or Li ₂ O.

[0013] Several investigations of problems associated with Li / air cells are described in, for example, Beattie, S .; , D. Monolescu, and S.M. Blair, “High-Capacity Lithium-Air Methods”, Journal of the Electrochemical Society, 2009.156, page A44, Kumar, B. et al. "A Solid-State, Rechargeable, Long Cycle Life Lithium-Air Battery", Journal of the Electrochemical Society, 2010.157, page A50, Read, J. et al. , “Characterization of the lithium / oxygen organic electrical battery”, Journal of the Electrochemical Society, 2002.149, A1190, Read, J. et al. “Oxygen transport properties of organic electrities and performance of lithium / oxygen battery”, Journal of the Electrochemical. And Y. Xia, “The effect of oxygen pressures on the electrochemical profile of lithium / oxygen battery”, Journal of Solid State Electro, 1 to 6 Et al., “Rechargeable Li ₂ O ₂ Electrode for Lithium Batteries”, Journal of the American Chemical Society, 2006.128 (4), pages 1390-1393. Nevertheless, some challenges have not yet been addressed for lithium / air cells. These challenges include limiting dendrite formation on lithium metal surfaces, protecting lithium metal (and possibly other materials) from air moisture and other potentially harmful components, Design a system that achieves the level of specific energy and power that is possible, reduce hysteresis between the charge and discharge voltages (which limit round-trip energy efficiency), and make the system reversible during that time May improve the number of cycles that can be cycled.

[0014] The round trip efficiency limitation occurs due to the obvious voltage hysteresis as shown in FIG. (3V approximately 2.5V relative to Li / Li ⁺⁾ 2 in the discharge voltage 40 is much lower than (4.5V approximately 4V with respect to Li / Li ⁺⁾ charge voltage 42. The equilibrium voltage 44 (or open circuit potential) of the lithium / air system is approximately 3V. The voltage hysteresis is therefore not only large but also very asymmetric.

[0015] The large overpotential during charging may be due to several causes. For example, the reaction between Li ₂ O ₂ and the conductive matrix 22 may form an insulating film between the two materials. In addition, there may be insufficient contact between the solid discharge product Li ₂ O ₂ or Li ₂ O and the electronic conductive matrix 22 of the positive electrode 14. Insufficient contact may occur as a result of oxidation of the discharge product directly adjacent to the conductive matrix 22 during charging, leaving a gap between the solid discharge product and the matrix 22.

  [0016] Another mechanism that provides inadequate contact between the solid discharge product and the matrix 22 is complete separation of the solid discharge product from the conductive matrix 22. Complete separation of the solid discharge product from the conductive matrix 22 may occur as a result of the rupture motion, delamination, or movement of the solid discharge product particles due to mechanical stress generated during cell charging / discharging. is there. Complete separation may contribute to the capacity decay observed for most lithium / air cells. As an example, FIG. 3 shows the discharge capacity of a typical Li / air cell over the duration of a charge / discharge cycle.

  Accordingly, what is needed is an energy storage system that can electrochemically recover isolated and / or poorly connected discharge particles. There is a further need for a lithium-based energy storage system that exhibits a reduced overpotential of the cell during charging operations.

  [0018] According to one embodiment, the electrochemical cell comprises a negative electrode comprising a form of lithium, a positive electrode comprising an electron conducting matrix with a gap between the negative electrode, a separator disposed between the negative electrode and the positive electrode, The electrolyte cell includes a salt-containing electrolyte and a charge redox couple located inside the positive electrode, and the electrochemical cell transfers electrons from the discharge product located at the positive electrode to the electron conducting matrix by the charge redox couple during the charge cycle. Features.

  [0019] In a further embodiment, the electrochemical cell comprises a negative electrode, a positive electrode including an electron conducting matrix with a gap between the negative electrode, a separator disposed between the negative electrode and the positive electrode, an electrolyte including a salt, and a positive electrode Including an internal charge redox couple, the electrochemical cell is characterized by the transfer of electrons from the electrically insulating discharge product located at the positive electrode to the electron conducting matrix by the charge redox couple during the charge cycle.

[0020] FIG. 1 is a schematic diagram of a prior art lithium ion cell including two electrodes and an electrolyte. [0021] Figure 2 is a charge / discharge curve for a normal Li / air electrochemical cell. [0022] FIG. 6 is a graph showing the decay of discharge capacity for a conventional Li / air electrochemical cell over several cycles. [0023] FIG. 1 is a schematic diagram of a lithium / air (Li / air) cell using two electrodes and a reservoir, the reservoir configured to exchange oxygen with the cathode for reversible reaction with lithium; Includes a concentrate of charge redox couple that acts as an electronic shuttle during charging of the Li / air cell. [0024] FIG. 5 is a schematic diagram of the Li / air cell of FIG. 4, where discharge products are formed in the conductive matrix of the positive electrode, with some separated discharge products located at the bottom of the positive electrode. [0025] FIG. 6 is a schematic view of the Li / air cell of FIG. 5, with a gap formed between the discharge product formed on the conductive matrix and the conductive matrix as a result of charging or discharging of the Li / air cell. Is done.

[0026] A schematic diagram of the electrochemical cell 100 is shown in FIG. The electrochemical cell 100 includes a negative electrode 102 that is isolated from a positive electrode 104 by a porous separator 106. The negative electrode 102 can be formed of lithium metal or a lithium insertion compound (eg, graphite, silicon, tin, LiAl, LiMg, Li ₄ Ti ₅ O ₁₂ ), but the Li metal is at the cell level compared to other candidate negative electrodes. Produces the highest specific energy.

  [0027] The positive electrode 104 in this embodiment includes a current collector 108 and carbon particles 110, which are optionally covered with a catalytic material and suspended within a porous matrix 112. The porous matrix 112 is a conductive matrix formed of a conductive material such as conductive carbon or nickel foam, although various alternative matrix structures and materials may be used. The separator 106 prevents the negative electrode 102 from being electrically connected to the positive electrode 104.

[0028] The electrochemical cell 100 includes an electrolyte solution 114 that resides in the positive electrode 104, and in some embodiments in the separator 106. In the exemplary embodiment of FIG. 4, electrolyte solution 114 includes a salt, LiPF ₆ (lithium hexafluorophosphate), dissolved in an organic solvent mixture. The organic solvent mixture can be any desired solvent. In certain embodiments, the solvent can be dimethyl ether (DME), acetonitrile (MeCN), ethylene carbonate, or diethyl carbonate.

  [0029] The barrier 116 isolates the positive electrode 104 from the reservoir 118. Reservoir 118 can be the atmosphere or can be any container suitable for holding oxygen and other gases supplied to and released from positive electrode 104. Although the reservoir 118 is shown as an integral part of the electrochemical cell 100 attached to the positive electrode 104, in alternative embodiments, a serpentine tube or other conduit is used to place the reservoir 118 in fluid communication with the positive electrode 104. There is. Various embodiments of the reservoir 118 are envisioned, including a rigid reservoir, an inflatable reservoir, and the like. In FIG. 4, the barrier 116 is a net that allows oxygen and other gases to flow between the positive electrode 104 and the reservoir 118, while further preventing the electrolyte 114 from leaving the positive electrode 104. To do.

[0030] The electrochemical cell 100 is capable of discharging in a state where the lithium metal in the negative electrode 102 is ionized into Li ⁺ ions along with free electrons e ⁻ . Li ⁺ ions travel through the separator 106 in the direction indicated by the arrow 120 and travel toward the positive electrode 104. Oxygen is supplied from reservoir 118 through barrier 116 as indicated by arrow 122. Free electrons e ⁻ flow into the positive electrode 104 through the current collector 108 as indicated by the arrow 124.

Referring to FIG. 5, oxygen atoms and Li ⁺ ions inside the positive electrode 102 are assisted by optional catalyst material on the carbon particles 110 to form a discharge product 130 inside the positive electrode 104. As can be seen from the following reaction formula, during the discharge process, metallic lithium is ionized and combined with oxygen and free electrons to form a Li ₂ O ₂ or Li ₂ O discharge product, which is a carbon particle. 110 surfaces can be coated.

  [0032] As the discharge continues, some of the discharge product 130 may flake off, or in some other transitions from the carbon particles 110 as illustrated by the separated discharge product 132. It may be removed.

[0033] The electrochemical cell 100 may be charged from a discharged state when desired. The electrochemical cell 100 can be charged by introducing an external current that oxidizes the Li ₂ O and Li ₂ O ₂ discharge products to lithium and oxygen. The internal current moves the lithium ions towards the negative electrode 102 where the Li ⁺ ions are reduced to metallic lithium, producing oxygen that diffuses through the barrier 116. The charging process is the reverse of the chemical reaction of the discharging process as shown by the following reaction formula.

[0034] The discharge product 130 in the form of Li ₂ O and Li ₂ O ₂ donates electrons that are transported to the current collector 108 by the conductive matrix 112 according to the foregoing reaction equation. This reaction can occur very rapidly with the discharge product 130 immediately adjacent to the particle 110 resulting in a gap 134, as shown in FIG. In some instances, the gap 134 may electrically insulate the discharge product 130 from the conductive matrix 112. In other instances, the gap 134 allows a portion of the discharge product 130 to flake off, resulting in increased isolated discharge product 132.

[0035] The gap 134 may further form as a result of charging the cell. As an example, Li ₂ O ₂ adjacent to the electronic conduction matrix reacts first due to the low electronic conductivity of Li ₂ O ₂ , thereby liberating O ₂ , Li + and electrons, and the conduction matrix There may be a case where a gap is left between the remaining Li ₂ O ₂ and the remaining Li ₂ O ₂ .

  [0036] Regardless of the mechanism by which isolated discharge product 132 or poorly connected discharge product 130 is formed, isolated discharge product 132 and poorly connected in electrochemical cell 100 Reduction of the discharge product 130 is enabled by the electrolyte solution 114. Specifically, the electrolyte solution 114 includes a charge oxidation-reduction pair, and the charge oxidation-reduction pair captures electrons from the discharge product 132 and the discharge product 130 as shown in the following reaction formula, Transported to the conductive matrix 112, where the charged redox couple is oxidized.

[0037] After the charge redox couple has been oxidized, it is possible to carry additional electrons 132 and additional electrons from the discharge product 130. In order to still provide the optimal performance of the charge redox couple, the charge redox couple is sufficient to function as a rapid redox shuttle between the discharge product 132, the discharge product 130, and the conductive matrix 112. The selected charge redox couple may exhibit high solubility in the electrolyte solution 114 to ensure that a concentrate is present in the electrolyte solution 114. When provided as an additive in the electrolyte solution 114, the charge redox couple is typically selected such that the charge redox couple does not react with the electrolyte, binder, separator, negative electrode, or current collector. . In one embodiment, the charged redox couple is a minor component of the electrolyte so that the charged redox couple does not adversely affect the electrolyte transport properties.

[0038] The performance of the electrochemical cell 100 is further optimized by proper selection of the equilibrium voltage of the charge redox couple. For example, the equilibrium voltages for Li ₂ O ₂ and Li ₂ O are 2.96V and 2.91V, respectively. Therefore, selecting an equilibrium voltage for the charge redox couple that is slightly higher than 2.96V, such as between 3V and 3.1V, limits the overpotential during cell charging.

  [0039] Exemplary classes of compounds that can be used as charge redox couples in electrochemical cell 100 include metallocenes (eg, ferrocene), halogens (eg, I- / I3-), and aromatic molecules (eg, tetramethyl). Phenylenediamine), but is not limited thereto. Some specific materials within the aforementioned class that are suitable for use in Li / air cells where the equilibrium voltage is between 2.9V and 4.5V include an equilibrium voltage of 3.05V. Ferrocene between 3 and 3.38V, n-butylferrocene with an equilibrium voltage between 3.18V and 3.5V, N, N-dimethylaminomethyl with an equilibrium voltage between 3.13V and 3.68V Ferrocene, 1,1-dimethylferrocene with an equilibrium voltage between 3.06V and 3.34V, 1,2,4-triazole sodium salt (NaTAZ) with an equilibrium voltage of 3.1V, and an equilibrium voltage of about 3 There is a lithium squat that is 1V.

  [0040] For a given embodiment, the charge redox couple may be selected to provide a high reversibility comparable to 100% coulomb efficiency. A highly reversible charge redox couple is desirable to allow the charge redox couple to be cycled many times during a single cell charge phase. Charged redox couples that exhibit fast dynamics (ie, high exchange current density) are also desirable. The high speed dynamics result in a smaller difference between the charge and discharge voltages of the charge redox couple, resulting in more efficient charging.

  [0041] As explained above, the activity of the charge redox couple is localized to the positive electrode. Thus, unlike overvoltage redox couples that are used to provide overvoltage protection and require high mobility to travel between the positive and negative electrodes, high mobility is required for charged redox couples is not. For example, movements on the order of tens of micrometers may be required when providing overvoltage protection, while the charged redox couple in the electrolyte solution 114 may travel about 1 μm or less.

[0042] If desired, a charge redox couple with high mobility can be used to act as a rapid redox shuttle between the discharge product 132, the discharge product 130, and the conductive matrix 112. High mobility charge redox couples can also be reduced at the negative electrode if unconstrained, so the transport of oxidizing species to the negative electrode can be prevented by applying a protective layer on the negative electrode. Thus, the charge redox couple is confined to the positive electrode and the separator. One material that can be used as a protective layer is Li _1.3 Ti _1.7 Al _0.3 (PO ₄ ), a lithium ion conducting glass-ceramic material commercially available from Rancha Santa Margarita, Ohara Corporation of California. ₃ .

[0043] By incorporating an optimally selected charging redox couple, the overpotential of the electrochemical cell 100 during charging is reduced. As an example, for the exemplary electrochemical cell 100 having a discharge product 130 and a separate discharge product 134 of Li ₂ O ₂ or Li ₂ O, the discharge product 130 and the separated discharge product. The equilibrium voltage of 134 is about 2.9V to 3V. By selecting the charge redox couple (R / R-), where the species R- is the reduced form of the species R) with an equilibrium voltage of 3.1 V, all of the charge redox couples are discharged during the cell When the voltage is lower than the equilibrium voltage of the discharge product, it will be in the reduced form (Species R-).

[0044] During charging of the exemplary electrochemical cell 100, the potential of the positive electrode relative to Li / Li + rises above 3.1 V, so that the reduced species R- is oxidized at the surface of the conductive matrix 112 to convert the species R. Will form. Species R can then react with the discharge products Li ₂ O ₂ or Li ₂ O (chemically or by a corrosion reaction) to form species R−, Li +, and O ₂ , because This is because the discharge product 130 and the separated discharge product 134 have an equilibrium voltage lower than the equilibrium voltage of the charged redox couple. The newly formed species R- can then impart its charge to the conducting matrix 112, while the liberated Li + can migrate towards the negative electrode 102 where it is deposited as Li metal. .

  [0045] Thus, a poorly connected discharge product 130 or even an isolated discharge product 134 can be consumed electrochemically during charging at a voltage that is only slightly higher than the voltage of the charge redox couple. . Assuming a discharge voltage of 2.8V, reducing the charging voltage from about 4V to about 3.2V can result in an increase in energy efficiency from 70% to over 87%.

  [0046] Although the invention has been illustrated and described in detail in the drawings and foregoing description, they are to be considered as illustrative and not restrictive in character. Only preferred embodiments have been presented and it is desired that all changes, modifications, and further applications within the spirit of the invention be protected.

[0046] Although the invention has been illustrated and described in detail in the drawings and foregoing description, they are to be considered as illustrative and not restrictive in character. Only preferred embodiments have been presented and it is desired that all changes, modifications, and further applications within the spirit of the invention be protected.
(Reference invention 1)
A negative electrode comprising a lithium form,
A positive electrode including an electron conductive matrix with a gap between the negative electrode,
A separator disposed between the negative electrode and the positive electrode;
An electrolyte comprising a salt, and
Charging redox couple located inside the positive electrode
An electrochemical cell comprising: an electron transferred from a discharge product located at the positive electrode to the electron conduction matrix by the charge redox couple during a charge cycle.
(Reference invention 2)
The electrochemical cell according to Reference Invention 1, wherein the charged redox couple is at least partially dissolved in the electrolyte.
(Reference invention 3)
The electrochemical cell according to Reference Invention 2, wherein the discharge product includes a first portion attached to the electron conducting matrix.
(Reference invention 4)
4. The electrochemical cell according to Reference Invention 3, wherein the discharge product includes a second portion physically separated from the electron conducting matrix.
(Reference invention 5)
The electrochemical cell according to Reference Invention 2, wherein the discharge product includes a form of oxygen.
(Reference invention 6)
The electrochemical cell according to Reference Invention 5, wherein the electron conductive matrix is porous and includes a plurality of carbon particles covered with a catalyst.
(Reference invention 7)
The electrochemical cell according to Reference Invention 2, wherein the charged redox couple includes one or more of a metallocene, a halogen, and an aromatic molecule.
(Reference Invention 8)
A protective layer between the negative electrode and the positive electrode configured to prevent transport of oxidized species of the charge redox couple to the negative electrode
The electrochemical cell according to Reference Invention 2, further comprising:
(Reference invention 9)
Negative electrode,
A positive electrode including an electron conductive matrix with a gap between the negative electrode,
A separator disposed between the negative electrode and the positive electrode;
An electrolyte comprising a salt, and
Charging redox couple located inside the positive electrode
An electrochemical cell comprising: an electrochemical cell, wherein electrons are transferred from the electrically insulating discharge product located at the positive electrode to the electron conducting matrix by the charge redox couple during a charge cycle. cell.
(Reference Invention 10)
The electrochemical cell according to Reference Invention 9, wherein the negative electrode includes a lithium form.
(Reference Invention 11)
The electrochemical cell according to Reference Invention 9, wherein the charged redox couple is at least partially dissolved in the electrolyte.
(Reference Invention 12)
The electrochemical cell according to Reference Invention 11, wherein the electrically insulating discharge product includes a first portion attached to the electron conducting matrix.
(Reference Invention 13)
13. The electrochemical cell according to Reference Invention 12, wherein the electrically insulating discharge product includes a second portion physically separated from the electron conducting matrix.
(Reference Invention 14)
The electrochemical cell according to Reference Invention 12, wherein the electrically insulating discharge product includes oxygen.
(Reference Invention 15)
The electrochemical cell according to Reference Invention 9, wherein the electron conductive matrix is porous and includes a plurality of carbon particles covered with a catalyst.
(Reference Invention 16)
The electrochemical cell according to Reference Invention 9, wherein the charged redox couple includes one or more of a metallocene, a halogen, and an aromatic molecule.
(Reference Invention 17)
A protective layer between the negative electrode and the positive electrode configured to prevent transport of oxidized species of the charge redox couple to the negative electrode
The electrochemical cell according to Reference Invention 9, further comprising:

Claims (17)

A negative electrode comprising a lithium form,
A positive electrode including an electron conductive matrix with a gap between the negative electrode,
A separator disposed between the negative electrode and the positive electrode;
An electrochemical cell comprising a salt-containing electrolyte, and a charge redox couple located inside the positive electrode, wherein the electron conduction matrix from a discharge product located at the positive electrode by the charge redox couple during a charge cycle Electrochemical cell characterized by transporting electrons to   The electrochemical cell of claim 1, wherein the charged redox couple is at least partially dissolved in the electrolyte.   The electrochemical cell of claim 2, wherein the discharge product includes a first portion attached to the electron conducting matrix.   The electrochemical cell of claim 3, wherein the discharge product comprises a second portion physically separated from the electron conducting matrix.   The electrochemical cell according to claim 2, wherein the discharge product includes a form of oxygen.   The electrochemical cell according to claim 5, wherein the electron conducting matrix is porous and includes a plurality of carbon particles covered with a catalyst.   The electrochemical cell according to claim 2, wherein the charged redox couple comprises one or more of a metallocene, a halogen, and an aromatic molecule. The electrochemical cell according to claim 2, further comprising a protective layer between the negative electrode and the positive electrode configured to prevent transport of oxidizing species of the charged redox couple to the negative electrode. Negative electrode,
A positive electrode including an electron conductive matrix with a gap between the negative electrode,
A separator disposed between the negative electrode and the positive electrode;
An electrolyte cell comprising a salt-containing electrolyte and a charge redox couple located inside the positive electrode, wherein the charge redox couple in a charge cycle causes the electric insulating discharge product located at the positive electrode to Electrochemical cell characterized in that it transports electrons to an electron conducting matrix.   The electrochemical cell according to claim 9, wherein the negative electrode includes a lithium form.   The electrochemical cell according to claim 9, wherein the charge redox couple is at least partially dissolved in the electrolyte.   The electrochemical cell of claim 11, wherein the electrically insulating discharge product includes a first portion attached to the electron conducting matrix. The electrically insulating discharge product is a second physically separated from the electron conducting matrix.
The electrochemical cell of claim 12, comprising:   The electrochemical cell according to claim 12, wherein the electrical insulating discharge product comprises oxygen.   The electrochemical cell of claim 9, wherein the electron conducting matrix is porous and includes a plurality of carbon particles covered with a catalyst.   The electrochemical cell according to claim 9, wherein the charged redox pair includes one or more of a metallocene, a halogen, and an aromatic molecule. The electrochemical cell according to claim 9, further comprising a protective layer between the negative electrode and the positive electrode configured to prevent transport of oxidizing species of the charge redox couple to the negative electrode.

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