Electrolyte, preparation method thereof and solid-state cathode primary lithium battery containing the electrolyte

Abstract

The application provides an electrolyte, a preparation method thereof and a solid cathode primary lithium battery containing the electrolyte. The electrolyte comprises an organic solvent, an electrolyte salt and an additive, the additive comprises a low-temperature type additive and a high-temperature type additive, the low-temperature type additive comprises propylene carbonate, the high-temperature type additive comprises 1,4-butanediol sulfone lactone, and the electrolyte salt comprises lithium bisfluorosulfonylimide and lithium perchlorate. The electrolyte of the solid cathode primary lithium battery provided by the application can expand the use temperature range of the battery to -40 DEG C to 150 DEG C, has good high and low temperature performance, has a higher low-temperature pulse voltage platform, and has high stability under high-temperature conditions.

Description

Technical Field

[0001] This invention relates to the field of lithium batteries, and more particularly to an electrolyte, a method for preparing the electrolyte, and a primary lithium battery containing the electrolyte as a solid cathode. Background Technology

[0002] Currently, solid-state cathode batteries made using commercially available electrolytes suffer from weak low-temperature pulse performance and poor high-temperature stability. While some commercially available low-temperature electrolytes for solid-state cathode batteries can meet low-temperature usage requirements, their composition and other factors prevent them from simultaneously ensuring high-temperature storage and safety. Furthermore, most commercially available high-temperature electrolytes for solid-state cathode batteries exhibit poor low-temperature performance, and the operating temperature of most solid-state cathode batteries on the market does not exceed 125°C, making prolonged use at high temperatures unsuitable. Currently, there is no solid-state cathode battery electrolyte on the market that simultaneously addresses both high and low-temperature performance.

[0003] Currently, many extreme environments, such as polar regions and desert areas, require batteries to operate within a wide temperature range. Globally and in various application scenarios, batteries can operate in temperatures ranging from -40°C to 100°C, and may even encounter temperatures exceeding 100°C. This necessitates that batteries maintain good discharge performance in both high and low temperature environments. The electrolyte is a key factor affecting battery discharge performance; therefore, for the aforementioned environments, it is necessary to research and develop electrolytes that are compatible with both high and low temperature performance.

[0004] CN 1567642A discloses a method for using a non-aqueous electrolyte containing halogenated olefin compounds as the electrolyte in a lithium secondary battery employing a graphite-based carbonaceous material as the negative electrode. During the initial charge, the compound additive decomposes earlier than the electrolyte's organic solvent, forming a dense and stable solid electrolyte interface film on the surface of the negative electrode. However, the non-aqueous electrolyte containing halogenated olefins poses a risk of releasing hydrogen halides when used at high battery temperatures, significantly reducing battery life.

[0005] CN112448034A discloses a non-aqueous electrolyte for high-voltage lithium batteries and a lithium battery thereof. The non-aqueous electrolyte for high-voltage lithium batteries includes a non-aqueous organic solvent, an electrolyte, and film-forming additives, wherein the film-forming additives contain negative electrode film-forming additives and fluorophosphate ester additives. However, it exhibits thermal expansion at high temperatures, which leads to increased battery impedance.

[0006] Therefore, how to prepare an electrolyte with compatible high and low temperature performance is an important research direction in this field. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide an electrolyte, a method for preparing the electrolyte, and a solid cathode primary lithium battery containing the electrolyte.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] One objective of this invention is to provide an electrolyte comprising an organic solvent, an electrolyte salt, and additives, wherein the additives include low-temperature additives and high-temperature additives, the low-temperature additives include propyl carbonate, the high-temperature additives include 1,4-butanesulfonyl lactone, and the electrolyte salts include lithium difluorosulfonylimide and lithium perchlorate.

[0010] This invention uses novel low-temperature additives to replace poorly soluble lithium salts such as lithium nitrate and lithium difluorophosphate. It also uses novel high-temperature additives to replace acid anhydrides that negatively impact low-temperature performance. The use of mixed lithium salts effectively improves the corrosion of aluminum current collectors by lithium difluorosulfonylimide, while significantly reducing the amount of lithium perchlorate used, thus mitigating battery safety and reliability issues caused by the strong oxidizing properties of lithium perchlorate. The low-temperature additives in this invention improve electrolyte performance at -40°C, and the high-temperature additives improve electrolyte performance above 150°C.

[0011] As a preferred embodiment of the present invention, the low-temperature additive further includes low-temperature ester solvents and / or lithium salt additives.

[0012] Preferably, the low-temperature ester solvent includes any one or a combination of at least two of fluoroethylene carbonate, vinyl sulfate, γ-butyrolactone, or vinylene carbonate, wherein typical but not limiting examples of the combination include: a combination of fluoroethylene carbonate and vinyl sulfate, a combination of vinyl sulfate and γ-butyrolactone, or a combination of γ-butyrolactone and vinylene carbonate, etc.

[0013] Preferably, the lithium salt additive includes lithium nitrate and / or lithium difluorophosphate.

[0014] As a preferred technical solution of the present invention, with the mass fraction of the electrolyte being 100%, the mass fraction of the low-temperature additive is 1 to 5%, wherein the mass fraction can be 1%, 2%, 3%, 4% or 5%, etc., but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0015] As a preferred embodiment of the present invention, the high-temperature additive further includes high-temperature ester solvents and / or acid anhydrides.

[0016] Preferably, the high-temperature ester solvent includes any one or a combination of at least two of ethylene carbonate, triargyl phosphate, 1,3-propanesulfonate lactone, or methanedisulfonate, wherein typical but non-limiting examples of the combination include: a combination of ethylene carbonate and triargyl phosphate, a combination of triargyl phosphate and 1,3-propanesulfonate lactone, or a combination of 1,3-propanesulfonate lactone and methanedisulfonate, etc.

[0017] Preferably, the acid anhydride includes phthalic anhydride and / or terephthalic anhydride.

[0018] As a preferred technical solution of the present invention, with the electrolyte having a mass fraction of 100%, the mass fraction of the high-temperature additive is 1-5%, wherein the mass fraction can be 1%, 2%, 3%, 4% or 5%, etc., but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0019] As a preferred embodiment of the present invention, the organic solvent includes a combination of at least two of propylene carbonate, ethylene carbonate, ethylene glycol dimethyl ether, methyl acetate, 1,3-dioxolane, or diethylene glycol dimethyl ether. Typical but non-limiting examples of such combinations include: a combination of propylene carbonate and ethylene carbonate, a combination of ethylene carbonate and ethylene glycol dimethyl ether, a combination of ethylene glycol dimethyl ether and methyl acetate, a combination of methyl acetate and 1,3-dioxolane, or a combination of 1,3-dioxolane and diethylene glycol dimethyl ether.

[0020] Preferably, with the electrolyte mass fraction as 100%, the organic solvent mass fraction is 75-89%, wherein the mass fraction can be 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, or 89%, etc., but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0021] As a preferred technical solution of the present invention, the mass ratio of lithium bis(fluorosulfonyl)imide to lithium perchlorate is (8-10):1, wherein the mass ratio can be 8:1, 9:1 or 10:1, etc., but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0022] Preferably, the electrolyte salt further includes a combination of at least two of lithium perchlorate, lithium difluorooxalate borate, lithium difluorosulfonylimide, lithium bis(trifluorosulfonylimide), or lithium trifluoromethanesulfonate, wherein typical but non-limiting examples of the combination include: a combination of lithium perchlorate and lithium difluorooxalate borate, a combination of lithium difluorooxalate borate and lithium difluorosulfonylimide, a combination of lithium difluorosulfonylimide and lithium bis(trifluorosulfonylimide), or a combination of lithium bis(trifluorosulfonylimide) and lithium trifluoromethanesulfonate, etc.

[0023] Preferably, with the electrolyte mass fraction being 100%, the mass fraction of the electrolyte salt is 9-15%, wherein the mass fraction can be 9%, 10%, 11%, 12%, 13%, 14%, or 15%, etc., but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0024] A second objective of this invention is to provide a method for preparing an electrolyte as described in one objective, characterized in that the preparation method comprises:

[0025] After adding an electrolyte salt to an organic solvent for the first mixing, an additive is then added to obtain the electrolyte solution.

[0026] As a preferred technical solution of the present invention, the temperature rise of the first mixture is <5°C, wherein the temperature rise can be 1°C, 2°C, 3°C, 4°C or 4.5°C, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0027] A third objective of this invention is to provide a solid-state cathode primary lithium battery, wherein the solid-state cathode primary lithium battery includes the electrolyte described in one objective.

[0028] The positive electrode material of the solid cathode primary lithium battery includes manganese dioxide, graphite, and acetylene black.

[0029] The solid-state cathode primary lithium battery used in this invention is a primary battery. This invention specifies the use of graphite and manganese dioxide materials as the positive electrode. The primary battery has a higher specific capacity and volumetric capacity than the secondary battery, but its internal resistance is much higher, resulting in a lower load capacity. The electrolyte in this invention is used in a primary battery with graphite-added manganese dioxide positive electrode material, which reduces the internal resistance of the primary battery and improves its safety and reliability.

[0030] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0032] The electrolyte of the solid cathode primary lithium battery provided in this invention can extend the battery's operating temperature range to -40℃ to 150℃, exhibiting good high and low temperature performance, a high low-temperature pulse voltage platform, and high stability under high-temperature conditions.

[0033] In this invention, a novel low-temperature additive, propyl carbonate, is used in the electrolyte, which has good solubility.

[0034] In this invention, a novel high-temperature additive, 1,4-butanesulfonyl lactone, is used in the electrolyte to replace high-temperature additives that have a negative impact on low-temperature performance.

[0035] This invention uses a mixed electrolyte salt, which can effectively improve the corrosion of aluminum current collectors by lithium bis(fluorosulfonyl)imide, while significantly reducing the amount of lithium perchlorate used, thus improving battery safety and reliability issues caused by the strong oxidizing properties of lithium perchlorate. Detailed Implementation

[0036] The technical solution of the present invention will be further illustrated below through specific embodiments.

[0037] Example 1

[0038] This embodiment provides a solid cathode primary lithium battery electrolyte:

[0039] In an argon-filled glove box with a moisture content of less than 1 ppm, the solvent components were mixed in proportion. Lithium salts were added steadily, slowly, and sequentially, ensuring the electrolyte temperature rise did not exceed 5°C. After the lithium salts were completely dissolved, the required amount of additives was added. The mixture was then shaken to obtain the desired electrolyte. Following the standard CR2032 coin cell manufacturing process, the prepared electrolyte was injected, and the manufactured CR2032 batteries underwent high and low temperature and capacity tests. The electrolyte salts included: 1% lithium perchlorate and 9% lithium difluorosulfonylimide; the organic solvents included: 42% propylene carbonate and 42% ethylene glycol dimethyl ether; the low-temperature additive included: 3% propyl carbonate; and the high-temperature additive included: 3% 1,4-butanesulfonyl lactone.

[0040] Example 2

[0041] This embodiment provides a solid cathode primary lithium battery electrolyte:

[0042] In an argon-filled glove box with a moisture content of less than 1 ppm, the solvent components were mixed in proportion. Lithium salts were added steadily, slowly, and sequentially, ensuring the electrolyte temperature rise did not exceed 5°C. After the lithium salts were completely dissolved, the required amount of additives was added. The mixture was then shaken well to obtain the desired electrolyte. Following the standard CR2032 coin cell manufacturing process, the prepared electrolyte was injected, and the fabricated CR2032 batteries underwent high and low temperature and capacity tests. The electrolyte salts were: lithium perchlorate 1%, lithium bis(fluorosulfonyl)imide 8%; organic solvents: ethylene carbonate 45%, methyl acetate 44%; high-temperature additive: BS 1%; low-temperature additive: propyl carbonate 1%.

[0043] Example 3

[0044] This embodiment provides a solid cathode primary lithium battery electrolyte:

[0045] In an argon glove box with a moisture content of less than 1 ppm, the solvent components were mixed in proportion. Lithium salts were added steadily, slowly, and sequentially, ensuring the electrolyte temperature rise did not exceed 5°C. After the lithium salts were completely dissolved, the required amount of additives was added. Finally, the mixture was shaken to obtain the desired electrolyte. The standard CR2032 coin cell manufacturing process was used, and the prepared electrolyte was injected. The fabricated CR2032 batteries underwent high and low temperature and capacity tests. The electrolyte salts were: lithium perchlorate 1%, lithium bis(fluorosulfonyl)imide 9%; organic solvents: 1,3-dioxolane 40%, diethylene glycol dimethyl ether 40%; high-temperature additive: BS 5%; low-temperature additive: propyl carbonate 5%.

[0046] Example 4

[0047] In this embodiment, the conditions are the same as in Example 1, except that the high-temperature additive 3% 1,4-butanesulfonyl lactone is replaced with 2% 1,4-butanesulfonyl lactone and 1% 1,3-propanesulfonyl lactone.

[0048] Example 5

[0049] In this embodiment, the conditions are the same as in Example 1, except that the high-temperature additive 3% 1,4-butanesulfonyl lactone is replaced with 2% 1,4-butanesulfonyl lactone and 1% triargyl phosphate.

[0050] Example 6

[0051] In this embodiment, the conditions are the same as in Example 1, except that the 3% propyl carbonate of the low-temperature additive is replaced with 1% lithium difluorophosphate and 2% propyl carbonate.

[0052] Example 7

[0053] In this embodiment, the only differences are that the lithium perchlorate content of 1% and the lithium difluorosulfonyl imide content of 9% are replaced with 6% and 9% lithium perchlorate and 9% lithium difluorosulfonyl imide content, and the propylene carbonate content of 42% is replaced with 37%. All other conditions are the same as in Example 1.

[0054] Example 8

[0055] In this embodiment, the only differences are that the lithium perchlorate content of 1% and the lithium difluorosulfonyl imide content of 9% are replaced with 1% and 14% lithium perchlorate and 42% lithium difluorosulfonyl imide, and the propylene carbonate content is replaced with 37%. All other conditions are the same as in Example 1.

[0056] Comparative Example 1

[0057] The conditions in this comparative example were the same as in Example 1, except that the high-temperature additive 3% 1,4-butanesulfonyl lactone was replaced with 3% 1,3-propanesulfonyl lactone.

[0058] Comparative Example 2

[0059] The conditions in this comparative example were the same as in Example 1, except that the high-temperature additive 3% 1,4-butanesulfonyl lactone was replaced with 3% phthalic anhydride.

[0060] Comparative Example 3

[0061] The conditions in this comparative example are the same as in Example 1, except that the 3% propyl carbonate of the low-temperature additive is replaced with 3% fluoroethylene carbonate.

[0062] Comparative Example 4

[0063] The conditions in this comparative example are the same as in Example 1, except that the 3% propyl carbonate low-temperature additive is replaced with 3% lithium nitrate.

[0064] Comparative Example 5

[0065] The comparative example is identical to Example 1 except that the electrolyte salts lithium perchlorate (1%) and lithium difluorosulfonyl imide (9%) are replaced with 10% lithium perchlorate.

[0066] Comparative Example 6

[0067] The only difference between this comparative example and Example 1 is that the electrolyte salt lithium perchlorate was 1% and the lithium difluorosulfonyl imide was 9%, which was replaced with 10% lithium difluorosulfonyl imide.

[0068] Comparative Example 7

[0069] The conditions for this comparative example are the same as those for Example 1, except that no low-temperature additive is added and the mass fraction of the high-temperature additive is replaced with 6%.

[0070] Comparative Example 8

[0071] This comparative example is identical to Example 1 except that no high-temperature additive is added and the mass fraction of the low-temperature additive is replaced with 6%.

[0072] Comparative Example 9

[0073] This comparative example uses a standard commercially available base electrolyte and conducts high and low temperature and capacity tests on the fabricated CR2032 batteries. The electrolyte salt is 10% lithium perchlorate; the organic solvents are 45% propylene carbonate and 45% ethylene glycol dimethyl ether; no additives are used.

[0074] Comparative Example 10

[0075] This comparative example uses commercially available high-temperature electrolyte for electrolyte filling, and the fabricated CR2032 batteries are subjected to high and low temperature and capacity tests. The electrolyte salt is 10% lithium perchlorate; the organic solvents are 43% propylene carbonate and 43% ethylene glycol dimethyl ether; the high-temperature additives are 2% 1,3-propanesulfonic acid lactone and 2% phthalic acid glycosides; no low-temperature additives are used.

[0076] Comparative Example 11

[0077] This comparative example uses a conventional commercially available low-temperature electrolyte for electrolyte filling, and the fabricated CR2032 batteries are subjected to high and low temperature and capacity tests. The electrolyte salt is 10% lithium perchlorate; the organic solvents are 30% propylene carbonate, 30% ethylene glycol dimethyl ether, and 30% 1,3-dioxolane; no additives are used.

[0078] Comparative Example 12

[0079] This comparative example uses a commercially available low-perchloride lithium electrolyte and conducts high and low temperature and capacity tests on the fabricated CR2032 batteries. The electrolyte salts are: 9% lithium trifluoromethanesulfonate and 1% lithium perchlorate; the organic solvents are: 45% propylene carbonate and 45% ethylene glycol dimethyl ether, with no additives.

[0080] The solid-state cathode primary lithium battery electrolytes prepared in Examples 1-8 and Comparative Examples 1-12 were injected into CR2032 coin cells. The positive electrode of the CR2032 coin cell consisted of manganese dioxide, graphite, and acetylene black in a mass ratio of 95:5:5, while the negative electrode was lithium metal. The prepared CR2032 cells were then subjected to high and low temperature tests and capacity tests. The test results are shown in Table 1.

[0081] Low temperature performance test method: Test 8mA continuous pulse voltage at -40℃ environment.

[0082] High-temperature performance testing methods: Test the changes in battery voltage, internal resistance and expansion rate after a 150℃ high-temperature shock, and perform an 8mA pulse test at -40℃ on the battery after the 150℃ shock.

[0083] Room temperature performance test: Test the battery discharge capacity at room temperature.

[0084] Table 1

[0085]

[0086]

[0087] From the table above, we can obtain:

[0088] Example 3 shows a high expansion rate after high-temperature impact due to the effect of the low-boiling-point 1,3-dioxolane. Example 3 also shows poor low-temperature performance due to the poor synergistic effect between diethylene glycol dimethyl ether and propylene carbonate. Examples 4-5 show that replacing 1,4-butanesulfonyl lactone with a combination of 1,4-butanesulfonyl lactone and other additives increases the internal resistance of the electrolyte and worsens high-temperature performance. Example 6 shows that replacing propyl carbonate with a combination of lithium difluorophosphate and propyl carbonate reduces high-temperature performance.

[0089] Examples 1-7 and Comparative Examples 1-4 demonstrate that propyl carbonate is a high-performance low-temperature additive that can replace poorly soluble lithium difluorophosphate and lithium nitrate, improving the low-temperature performance of batteries. In Comparative Examples 2-3, the film-forming effect of phthalic anhydride and fluoroethylene carbonate resulted in voltage hysteresis and reduced low-temperature performance.

[0090] As can be seen from Examples 1, 7-8 and Comparative Examples 5-6, the amount of lithium perchlorate and lithium difluorosulfonylimide added should not be too much. The effect of using the two together is the best, and the proportion should not exceed 10%, otherwise it will cause the high and low temperature performance of the battery to be reduced.

[0091] As can be seen from Examples 1-8 and Comparative Examples 1-8, 1,4-butanesulfonyl lactone can replace 1,3-propanesulfonyl lactone, methylene methanedisulfonate, and phthalic anhydride, which has a negative impact on low temperature, and can also work together to inhibit expansion and gas production. The more it is added, the more obvious the effect of inhibiting expansion will be, but the low temperature pulse performance will gradually deteriorate.

[0092] As can be seen from Comparative Example 8, the amount of propyl carbonate added should not be too much. Too much addition will reduce its low-temperature pulse performance, and without the addition of high-temperature additives, its high-temperature performance will also be worse.

[0093] Comparative Examples 9-12 are four commercially available electrolytes. Comparative Examples 1-2 show good low-temperature performance, but due to the excessive addition of low-boiling-point 1,3-dioxolane, they expand severely under high-temperature shock. Comparative Example 10, with the addition of additives to inhibit gas production and expansion, shows good high-temperature performance, but relatively poor low-temperature performance. Comparative Examples 9 and 12, two conventional electrolytes and a low-perchloride lithium electrolyte, exhibit moderate low-temperature performance but poor high-temperature performance, resulting in gas production and severe expansion.

[0094] The capacity mainly depends on the positive electrode active material and the battery manufacturing process. The room temperature discharge capacity of the various electrolytes is not significantly different, which proves that the wide-temperature electrolyte of this invention does not reduce the battery's discharge capacity. The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of this invention. It should be understood that the above descriptions are merely specific embodiments of this invention and are not intended to limit the invention. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A solid cathode primary lithium battery electrolyte, characterized in that, The electrolyte includes an organic solvent, an electrolyte salt, and additives. The additives include low-temperature additives and high-temperature additives. The low-temperature additive includes propyl carbonate, and the high-temperature additive includes 1,4-butanesulfonyl lactone. The electrolyte salts include lithium difluorosulfonylimide and lithium perchlorate. Based on the electrolyte mass fraction of 100%, the mass fraction of the low-temperature additive is 1~4%, and the mass fraction of the high-temperature additive is 1~4%. The mass ratio of lithium bis(fluorosulfonyl)imide to lithium perchlorate is (8~10):

1.

2. The solid cathode primary lithium battery electrolyte according to claim 1, characterized in that, The low-temperature additives also include low-temperature ester solvents and / or lithium salt additives.

3. The solid cathode primary lithium battery electrolyte according to claim 2, characterized in that, The low-temperature ester solvent includes any one or a combination of at least two of fluoroethylene carbonate, ethylene sulfate, γ-butyrolactone, or vinylene carbonate.

4. The solid cathode primary lithium battery electrolyte according to claim 2, characterized in that, The lithium salt additives include lithium nitrate and / or lithium difluorophosphate.

5. The solid cathode primary lithium battery electrolyte according to claim 1, characterized in that, The high-temperature additives also include high-temperature ester solvents and / or acid anhydrides.

6. The solid cathode primary lithium battery electrolyte according to claim 5, characterized in that, The high-temperature ester solvent includes any one or a combination of at least two of ethylene carbonate, triargyl phosphate, 1,3-propanesulfonate lactone, or methanedisulfonate.

7. The solid cathode primary lithium battery electrolyte according to claim 5, characterized in that, The acid anhydrides include phthalic anhydride and / or terephthalic anhydride.

8. The solid cathode primary lithium battery electrolyte according to claim 1, characterized in that, The organic solvent includes a combination of at least two of propylene carbonate, ethylene carbonate, ethylene glycol dimethyl ether, methyl acetate, 1,3-dioxolane, or diethylene glycol dimethyl ether.

9. The solid cathode primary lithium battery electrolyte according to claim 1, characterized in that, With the electrolyte having a mass fraction of 100%, the organic solvent has a mass fraction of 75-89%.

10. The solid cathode primary lithium battery electrolyte according to claim 1, characterized in that, The electrolyte salt also includes a combination of at least two of lithium difluorooxalate borate, lithium bis(trifluorosulfonyl)imide, or lithium trifluoromethanesulfonate.

11. The solid cathode primary lithium battery electrolyte according to claim 1, characterized in that, With the electrolyte mass fraction being 100%, the mass fraction of the electrolyte salt is 9-15%.

12. A method for preparing a solid cathode primary lithium battery electrolyte as described in any one of claims 1-11, characterized in that, The preparation method includes: After adding an electrolyte salt to an organic solvent for the first mixing, additives are then added to obtain the solid cathode primary lithium battery electrolyte.

13. The preparation method according to claim 12, characterized in that, The temperature rise of the first mixture is less than 5°C.

14. A solid-state cathode primary lithium battery, characterized in that, The solid cathode primary lithium battery includes the solid cathode primary lithium battery electrolyte as described in any one of claims 1-11; The positive electrode material of the solid cathode primary lithium battery includes manganese dioxide, graphite, and acetylene black.

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