NON-AQUEOUS ELECTROLYTES FOR ENHANCED BATTERY SHELF-LIFE
20250349892 ยท 2025-11-13
Inventors
Cpc classification
Y02E60/10
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
International classification
H01M4/583
ELECTRICITY
Abstract
Certain aspects of the present disclosure may include a battery including a cathode including a fluorinated carbon material and manganese oxide, an anode including one or more of a lithium metal or a lithium alloy, and a non-aqueous electrolyte including: an organic solvent, one or more lithium salts including lithium perchlorate, and an additive material having lithium nitrate and tris-trimethyl silyl phosphite.
Claims
1. A battery, comprising: a cathode including a fluorinated carbon material and manganese oxide; an anode including one or more of a lithium metal or a lithium alloy; and a non-aqueous electrolyte including: an organic solvent including propylene carbonate (PC), dimethyl carbonate (DME), and tetrahydrofuran (THF); one or more lithium salts including lithium perchlorate dissolved in the organic solvent; and an additive material having lithium nitrate and tris-trimethyl silyl phosphite.
2. The battery of claim 1, wherein the lithium nitrate is between 0.05 weight percent to 0.6 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
3. The battery of claim 1, wherein the tris-trimethyl silyl phosphite is between 0.5 weight percent to 8 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
4. The battery of claim 1, wherein the organic solvent includes at least one of a carbonate, an ether, a cyclic carbonate, a glyme, or a cyclic ether.
5. The battery of claim 1, wherein the one or more lithium salts further includes at least one of LiPF.sub.6, LiSbF.sub.6, LiBF.sub.4, LiTFSI, LiFSI, LiAlCl.sub.4, LiASF.sub.6, LiClO.sub.4, LiGaCl.sub.4, LiC(S0.sub.2CF.sub.3).sub.3, LiN(CF.sub.3SO.sub.2).sub.2, Li(CF.sub.3SO.sub.3), or LiB(C.sub.6H.sub.4O.sub.2).sub.2.
6. The battery of claim 1, wherein: the fluorinated carbon material is between 5 weight percent and 95 weight percent, inclusive, of a total weight of the cathode; and the manganese oxide is between 5 weight percent and 40 weight percent, inclusive, of the total weight of the cathode.
7. The battery of claim 1, wherein the manganese oxide is MnO.sub.2.
8. The battery of claim 1, further comprising a separator.
9. The battery of claim 1, wherein the lithium nitrate is between 0.17 weight percent and 0.34 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
10. The battery of claim 9, wherein the tris-trimethyl silyl phosphite is 2.0 weight percent, inclusive, of the total weight of the non-aqueous electrolyte.
11. The battery of claim 1, wherein a form factor of the batter is a prismatic form factor, a pouch form factor, or a cylindrical form factor.
12. A method of manufacturing a battery, comprising: forming one of a cathode or an anode, the cathode including a fluorinated carbon material and manganese oxide and the anode including one or more of a lithium metal or a lithium alloy; forming the other of the anode or the cathode; and adding a non-aqueous electrolyte between the cathode and the anode, the non-aqueous electrolyte including an organic solvent including propylene carbonate (PC), dimethyl carbonate (DME), and tetrahydrofuran (THF), one or more lithium salts including lithium perchlorate dissolved in the organic solvent, and an additive material having lithium nitrate and tris-trimethyl silyl phosphite to the battery.
13. The method of claim 12, wherein the lithium nitrate is between 0.05 weight percent to 0.6 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
14. The method of claim 12, wherein the tris-trimethyl silyl phosphite is between 0.5 weight percent to 8 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
15. The method of claim 12, wherein the organic solvent includes at least one of a carbonate, an ether, a cyclic carbonate, a glyme, or a cyclic ether.
16. The method of claim 12, wherein the one or more lithium salts further includes at least one of LiPF.sub.6, LiSbF.sub.6, LiBF.sub.4, LiTFSI, LiFSI, LiAlCl.sub.4, LiAsF.sub.6, LiC1O.sub.4, LiGaCl.sub.4, LiC(SO.sub.2CF.sub.3).sub.3, LiN(CF.sub.3SO.sub.2).sub.2, Li(CF.sub.3SO.sub.3), or LiB(C.sub.6H.sub.4O.sub.2).sub.2.
17. The method of claim 12, wherein: the fluorinated carbon material is between 5 weight percent and 95 weight percent, inclusive, of a total weight of the cathode; and the manganese oxide is between 5 weight percent and 40 weight percent, inclusive, of the total weight of the cathode.
18. The method of claim 12, wherein the manganese oxide is MnO.sub.2.
19. The method of claim 12, wherein the lithium nitrate is between 0.17 weight percent and 0.34 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
20. The battery of claim 19, wherein the tris-trimethyl silyl phosphite is 2.0 weight percent, inclusive, of the total weight of the non-aqueous electrolyte.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The features believed to be characteristic of aspects of the disclosure are set forth in the appended claims. In the description that follows, like parts are marked throughout the specification and drawings with the same numerals, respectively. The drawing figures are not necessarily drawn to scale and certain figures may be shown in exaggerated or generalized form in the interest of clarity and conciseness. The disclosure itself, however, as well as a preferred mode of use, further objects, and advantages thereof, will be best understood by reference to the following detailed description of illustrative aspects of the disclosure when read in conjunction with the accompanying drawings, wherein:
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DETAILED DESCRIPTION
[0026] The following includes definitions of selected terms employed herein. The definitions include various examples and/or forms of components that fall within the scope of a term and that may be used for implementation. The examples are not intended to be limiting.
[0027] Among the several methods used for mitigating battery performance degradation, the use of electrolytes additives is an effective method as they can scavenge the unwanted species in the system and/or form a desired solid electrolyte interphase. Furthermore, nitrate and phosphite additives were used in the various electrochemical systems alone and in combination with other electrolyte additives.
[0028] Certain additives or combination additives described in prior art references may be insufficient in combating the deterioration of battery shelf-life, especially after accelerated storage studies. For example, none of the prior art discloses using both nitrate and phosphite additive in low amount, which shows unexpected results as described in the detailed descriptions below. Further, the prior art references disclose rechargeable batteries or secondary batteries, not one-time use battery. Additionally, none of the prior art references discloses an organic solvent including propylene carbonate (PC), dimethyl carbonate (DME), and tetrahydrofuran (THF). Furthermore, when a combination of CF.sub.X and MnO.sub.2 active material is used, adding LiNO.sub.3 additive alone in the electrolyte was not observed to improve shelf life and low temperature performance. Therefore, improvements may be desirable as the battery chemistry and electrolyte system were different.
[0029] In certain aspects of the present disclosure, when nitrate and phosphites were used in the system alone, minimal improvement in the battery shelf life were observed. Meanwhile, extended shelf-life of the batteries were observed as an unexpected result when both the additives were used together, so there is a synergic effect that help providing the extended shelf life and low temperature performance.
[0030] Aspects of the present disclosure include a battery including a cathode including a fluorinated carbon material and manganese dioxide, an anode including one or more of a lithium metal or a lithium alloy, and a non-aqueous electrolyte including: an organic solvent, one or more lithium salts including lithium perchlorate, and an additive material having lithium nitrate and tris-trimethyl silyl phosphite.
[0031]
[0032] During a charge operation (if available), the reverse redox process occurs. An external power supply (not shown) provides electrical energy to the battery 100, which is stored electrochemically. Here, an oxidation process occurs at the cathode 102 and positive ions move from the cathode 102 into the electrolyte 110. A reduction process occurs at the anode 106 and the positive ions in the electrolyte 110 move from the electrolyte 110 toward the anode 106. This charge operation restores the electrochemical energy of the battery 100, enabling it to provide electrical energy in a subsequent discharge operation.
[0033] In some aspects of the present disclosure, the battery 100 may include a separator 120 configured to prevent electrical contact and physical contact between the cathode 102 and the anode 106. The battery 100 may include one or more of current collectors, terminals, and/or casings that are not shown in
[0034] In some aspects of the present disclosure, the cathode 102 may include one or more of a fluorinated carbon (i.e., CF.sub.X) or a metal oxide material such as manganese oxide, copper oxide, bismuth oxide, tin oxide, zinc oxide, or other suitable materials. In certain aspects, the fluorinated carbon may range from 5 to 95 weight percent, inclusive, of the total weight of the cathode 102. The metal oxide may range from 5 to 90 weight of the total weight of the cathode 102. Other weight percentages for the fluorinated carbon and/or the metal oxide may also be implemented according to aspects of the present disclosure. In one exemplary aspect, the cathode 102 may include a fluorinated carbon and a manganese oxide such as MnO.sub.2.
[0035] In one aspect of the present disclosure, the anode 106 may include one or more of a lithium metal or a lithium alloy. In some aspects, the lithium alloy may include lithium with one or more of magnesium, potassium, or sodium. The anode 106 may include one or more of a lithium aluminum alloy, lithium silicon alloy, lithium tin alloy, a lithium carbon material, a LiSn.sub.2O.sub.3 material, or a LiSnO.sub.2 material. Other suitable materials may also be used. The anode 106 may be configured with materials in the form of foils or pressed-powder sheets. The anode 106 may include one or more of a current collector or a protective layer.
[0036] In one aspect of the present disclosure, the electrolyte 110 may be non-aqueous. The electrolyte may include one or more solvents and/or one or more salts. The one or more solvents may include one or more of an organic solvent such as a carbonate, an ether, a cyclic carbonate, a glyme, or a cyclic ether. The one or more salts may include one or more of a lithium salt such as LiPF.sub.6, LiSbF.sub.6, LiBF.sub.4, LiTFSI, LiFSI, LiAlCl.sub.4, LiAsF.sub.6, LiClO.sub.4, LiGaCl.sub.4, LiC(SO.sub.2CF.sub.3).sub.3, LiN(CF.sub.3SO.sub.2).sub.2, Li(CF.sub.3SO.sub.3), LiNO.sub.3 or LiB(C.sub.6H.sub.4O.sub.2).sub.2.
[0037] In an aspect, the electrolyte 110 may be a non-aqueous electrolyte having lithium perchlorate (LiClO.sub.4) with a concentration of LiClO.sub.4 between one of 0.1 to 1.4 molarity range, 0.15 to 1.3 molarity range, or 0.2 to 1.25 molarity range. The non-aqueous electrolyte may include LiClO.sub.4 salt dissolved in one or more of Propylene carbonate (PC), Dimethyl carbonate (DME), or Tetrahydrofuran (THF). Other concentration may also be used according to aspects of the present disclosure.
[0038] In some aspects of the present disclosure, the electrolyte 110 may include one or more additives. In some aspects, the one or more additives may include a phosphorous-containing additive such as phosphite, a tris-trimethyl silyl phosphite (TMSPi), or other suitable materials. In certain aspects, the one or more additives may include a lithium based additive such as lithium nitrate or other suitable materials.
[0039] Aspects of the present disclosure include the electrolyte 110 having any one of or any combination of the additives indicated above, with any weight percentage(s). For example, the phosphorous-containing additive may range from one of 0.1 to 10 weight percent, 0.25 to 9 weight percent, or 0.5 to 8 weight percent, inclusive, of the total weight of the electrolyte 110. In another example, the lithium nitrate may range from one of 0.01 to 0.8 weight percent, 0.025 to 0.7 weight percent, 0.5 to 0.6, or 0.05 to 0.6 weight percent, inclusive, of the total weight of the electrolyte 110.
[0040] In some aspects of the present disclosure, the battery 100 and at least some components of the battery 100 may be self-contained within a sealed cell housing, such as the compartment 104. The battery 100 may be manufactured as different form factors and materials, including prismatic, pouch and cylindrical (e.g., double A, triple A, C, D-sizes).
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[0047] Here, the battery cells with the baseline electrolyte, with LiNO.sub.3 only, and with TMSPi only fail to show any improvements in the discharge voltage after long term storage. Since the battery cells with LiNO.sub.3 only and with TMSPi only fail to show any improvements in discharge voltage after long term storage, one skilled in the art would not expect to use a combination of LiNO.sub.3 and TMSPi in the additive to improve the discharge voltage.
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[0049] At 505, the method 500 may include adding one of a cathode or an anode, the cathode including a fluorinated carbon material and manganese oxide and the anode including one or more of a lithium metal or a lithium alloy. One or more of a mixer for mixing the electrode slurry, a coater for coating the slurry on a flat surface, a roller for calendaring the coated rolls of the slurry, a cutter for slitting the electrode foils after the calendaring, and/or a stacker for embedding the cathode and/or the anode into battery cell may be configured to, and/or provide the means for, adding one of a cathode or an anode, the cathode including a fluorinated carbon material and manganese oxide and the anode including one or more of a lithium metal or a lithium alloy.
[0050] At 510, the method 500 may include adding the other of the anode or the cathode. One or more of a mixer for mixing the electrode slurry, a coater for coating the slurry on a flat surface, a roller for calendaring the coated rolls of the slurry, a cutter for slitting the electrode foils after the calendaring, and/or a stacker for embedding the cathode and/or the anode into battery cell may be configured to, and/or provide the means for, adding the other of the anode or the cathode.
[0051] At 515, the method 500 may include adding a non-aqueous electrolyte, the non-aqueous electrolyte including an organic solvent, one or more lithium salts including lithium perchlorate, and an additive material having lithium nitrate and tris-trimethyl silyl phosphite to the battery. A mixer may be configured to, and/or provide means for, adding a non-aqueous electrolyte, the non-aqueous electrolyte including an organic solvent, one or more lithium salts including lithium perchlorate, and an additive material having lithium nitrate and tris-trimethyl silyl phosphite to the battery.
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[0057] Aspects of the present disclosure include a battery including a cathode including a fluorinated carbon material and manganese oxide, an anode including one or more of a lithium metal or a lithium alloy, a non-aqueous electrolyte including an organic solvent including propylene carbonate (PC), dimethyl carbonate (DME), and tetrahydrofuran (THF), one or more lithium salts including lithium perchlorate dissolved in the organic solvent, and an additive material having lithium nitrate and tris-trimethyl silyl phosphite.
[0058] Aspects of the present disclosure include the battery above, wherein the lithium nitrate is between 0.05 weight percent to 0.6 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
[0059] Aspects of the present disclosure include any of the batteries above, wherein the tris-trimethyl silyl phosphite is between 0.5 weight percent to 8 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
[0060] Aspects of the present disclosure include any of the batteries above, wherein the organic solvent includes at least one of a carbonate, an ether, a cyclic carbonate, a glyme, or a cyclic ether.
[0061] Aspects of the present disclosure include any of the batteries above, wherein the one or more lithium salts further includes at least one of LiPF.sub.6, LiSbF.sub.6, LiBF.sub.4, LiTFSI, LiFSI, LiAlCl.sub.4, LiAsF.sub.6, LiClO.sub.4, LiGaCl.sub.4, LiC(S0.sub.2CF.sub.3).sub.3, LiN(CF.sub.3SO.sub.2).sub.2, Li(CF.sub.3SO.sub.3), or LiB(C.sub.6H.sub.4O.sub.2).sub.2.
[0062] Aspects of the present disclosure include any of the batteries above, wherein the fluorinated carbon material is between 5 weight percent and 95 weight percent, inclusive, of a total weight of the cathode and the manganese oxide is between 5 weight percent and 40 weight percent, inclusive, of the total weight of the cathode.
[0063] Aspects of the present disclosure include any of the batteries above, wherein the manganese oxide is MnO.sub.2.
[0064] Aspects of the present disclosure include any of the batteries above, further comprising a separator.
[0065] Aspects of the present disclosure include any of the batteries above, wherein the lithium nitrate is between 0.17 weight percent and 0.34 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
[0066] Aspects of the present disclosure include any of the batteries above, wherein the tris-trimethyl silyl phosphite is 2.0 weight percent, inclusive, of the total weight of the non-aqueous electrolyte.
[0067] Aspects of the present disclosure include any of the batteries above, wherein a form factor of the batter is a prismatic form factor, a pouch form factor, or a cylindrical form factor.
[0068] Aspects of the present disclosure include a method of manufacturing a battery including forming one of a cathode or an anode, the cathode including a fluorinated carbon material and manganese oxide and the anode including one or more of a lithium metal or a lithium alloy, forming the other of the anode or the cathode, and adding a non-aqueous electrolyte between the cathode and the anode, the non-aqueous electrolyte including an organic solvent including propylene carbonate (PC), dimethyl carbonate (DME), and tetrahydrofuran (THF), one or more lithium salts including lithium perchlorate dissolved in the organic solvent, and an additive material having lithium nitrate and tris-trimethyl silyl phosphite to the battery.
[0069] Aspects of the present disclosure include the method above, wherein the lithium nitrate is between 0.05 weight percent to 0.6 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
[0070] Aspects of the present disclosure include any of the methods above, wherein the tris-trimethyl silyl phosphite is between 0.5 weight percent to 8 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
[0071] Aspects of the present disclosure include any of the methods above, wherein the organic solvent includes at least one of a carbonate, an ether, a cyclic carbonate, a glyme, or a cyclic ether.
[0072] Aspects of the present disclosure include any of the methods above, wherein the one or more lithium salts further includes at least one of LiPF.sub.6, LiSbF.sub.6, LiBF.sub.4, LiTFSI, LiFSI, LiAlCl.sub.4, LiAsF.sub.6, LiC1O.sub.4, LiGaCl.sub.4, LiC(SO.sub.2CF.sub.3).sub.3, LiN(CF.sub.3SO.sub.2).sub.2, Li(CF.sub.3SO.sub.3), or LiB(C.sub.6H.sub.4O.sub.2).sub.2.
[0073] Aspects of the present disclosure include any of the methods above, wherein the fluorinated carbon material is between 5 weight percent and 95 weight percent, inclusive, of a total weight of the cathode and the manganese oxide is between 5 weight percent and 40 weight percent, inclusive, of the total weight of the cathode.
[0074] Aspects of the present disclosure include any of the methods above, wherein the manganese oxide is MnO.sub.2.
[0075] Aspects of the present disclosure include any of the methods above, wherein the lithium nitrate is between 0.17 weight percent and 0.34 weight percent, inclusive, of a total weight of the non-aqueous electrolyte.
[0076] Aspects of the present disclosure include any of the methods above, wherein the tris-trimethyl silyl phosphite is 2.0 weight percent, inclusive, of the total weight of the non-aqueous electrolyte.
[0077] It will be appreciated that various implementations of the above-disclosed and other features and functions, or alternatives or varieties thereof, may be desirably combined into many other different systems or applications. Also, that various presently unforeseen or unanticipated alternatives, modifications, variations, or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims.