阅读说明：本技术 一种锂一次电池电解液及其制备方法和应用 (Lithium primary battery electrolyte and preparation method and application thereof ) 是由 黄杰 董亚楠 李文俊 李泓 俞会根 于 2019-03-27 设计创作，主要内容包括：本发明提供了一种锂一次电池电解液,包括有机溶剂、添加剂、其他添加剂和锂盐,所述添加剂包括Li<Sub>2</Sub>S<Sub>x</Sub>、R<Sub>1</Sub>-S-R<Sub>2</Sub>、R<Sub>1</Sub>-S-S-R<Sub>2</Sub>和R<Sub>1</Sub>-S-S-S-R<Sub>2</Sub>中的任意一种或两种以上的混合物,其中,x＝2-8,R、R<Sub>1</Sub>和R<Sub>2</Sub>分别选自烷基、烯基、炔基、芳香基、卤代烷基、醛基和羧基中的其中一种。本发明通过加入有机或无机多硫化物作为锂一次电解液的添加剂,可以使锂一次电池在正极放电完成后还可继续还原放电提供容量,显著提高锂一次电池的能量密度；本发明还提供了该电解液的制备方法,该方法操作简单,实用性强且应用范围广。(The invention provides an electrolyte of a lithium primary battery, which comprises an organic solvent, an additive, other additives and a lithium salt, wherein the additive comprises Li 2 S x 、R 1 ‑S‑R 2 、R 1 ‑S‑S‑R 2 And R 1 ‑S‑S‑S‑R 2 Any one or a mixture of two or more of them, wherein x is 2-8, R, R 1 And R 2 Respectively selected from one of alkyl, alkenyl, alkynyl, aryl, halogenated alkyl, aldehyde group and carboxyl. According to the invention, organic or inorganic polysulfide is added as an additive of the lithium primary electrolyte, so that the lithium primary battery can continue to reduce and discharge to provide capacity after the positive electrode discharge is finished, and the energy density of the lithium primary battery is obviously improved; the invention also provides a preparation method of the electrolyte, and the method is simple to operate, strong in practicability and wide in application range.)

1. A lithium primary battery electrolyte comprising an organic solvent, an additive, a further additive and a conductive lithium salt, wherein the additive comprises Li₂S_x、R₁-S-R₂、R₁-S-S-R₂And R₁-S-S-S-R₂Any one or a mixture of two or more of them, wherein x is 2-8, R, R₁And R₂Respectively selected from one of alkyl, alkenyl, alkynyl, aryl, halogenated alkyl, aldehyde group and carboxyl.

2. The lithium primary battery electrolyte of claim 1 wherein the additive is present in an amount of 0.5 to 50% by mass based on the total mass of the lithium primary battery electrolyte.

3. The lithium primary battery electrolyte according to claim 1, wherein the organic solvent includes any one or a mixture of two or more of tetraglyme, dimethoxyethane, 1, 3-dioxolane, ethylene glycol dimethyl ether, diglyme, diethylene glycol dimethyl ether, 2-methyltetrahydrofuran, cyclohexane, cyclohexyl ether, tetrahydrofuran, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, methyl carbonate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl butyrate, dimethylene sulfoxide, dimethyl sulfone, methyl ethyl sulfone, and sulfolane.

4. The lithium primary battery electrolyte of claim 1, wherein the conductive lithium salt is selected from any one or a mixture of two or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (trifluorosulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium nitrate, lithium tetrachloroaluminate, and lithium trifluoromethanesulfonate.

5. The lithium primary battery electrolyte of claim 4, wherein the concentration of the conductive lithium salt in the lithium primary battery electrolyte is 0.1-2 mol/L.

6. The lithium primary battery electrolyte of claim 1, wherein the other additive is any one or a mixture of two or more of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, 1,3- (1-propene) sultone, ethylene sulfite, vinyl sulfate, dimethyl sulfate, diethyl sulfate, propylene sulfate, ethylene sulfite, ethylene carbonate, propylene sulfite, butylene sulfite, dimethyl sulfoxide, sulfolane, acetonitrile, succinonitrile, adiponitrile, and glutaronitrile.

7. The method of preparing the electrolyte for a lithium primary battery according to any one of claims 1 to 6, comprising the steps of: under the protection of inert gas, mixing organic solvent, additive, other additives and conductive lithium salt, and uniformly stirring to obtain the lithium primary battery electrolyte.

8. A lithium primary battery comprising the lithium primary battery electrolyte according to any one of claims 1 to 7.

9. The lithium primary battery according to claim 8, wherein the lithium primary battery is any one of a lithium/graphite fluoride battery, a lithium/manganese dioxide battery, and a lithium/ferrous sulfide battery.

10. The lithium primary battery of claim 8, further comprising a positive electrode, wherein the additive in the electrolyte of the lithium primary battery continues to reduce and discharge to provide capacity after discharge of the positive electrode of the lithium primary battery is complete.

[ technical field ] A method for producing a semiconductor device

The invention relates to the technical field related to lithium battery electrolyte, in particular to lithium primary battery electrolyte and a preparation method and application thereof.

[ background of the invention ]

With the rapid development of electronic information technology and consumer electronics, the performance requirements for batteries are also rapidly increasing, especially the energy density of batteries, which has become a key technical difficulty encountered in the expansion of the application field of lithium primary batteries. At present, the types of metal lithium primary batteries are various, the metal lithium primary batteries have higher energy ratio and working voltage, the developed systems mainly comprise lithium/carbon fluoride batteries, lithium/manganese dioxide batteries, lithium/thionyl chloride batteries, lithium/sulfur dioxide batteries and the like, the energy density can generally reach 250-350Wh/kg, and the ever-increasing requirements can not be met.

The typical formulation of conventional electrolytes of current lithium primary batteries is: the electrolyte is lithium hexafluorophosphate (LiPF6), the solvent is propylene carbonate and dimethyl carbonate, the capacity of the battery cannot be contributed, and a plurality of problems exist in the practical application process, and the battery containing the electrolyte generally has the problems of small discharge current density, poor rate discharge performance, low discharge platform, small energy density and the like.

[ summary of the invention ]

Aiming at the technical problems in the prior art, the invention provides the lithium primary battery electrolyte, inorganic or organic polysulfide and the like are added into the common electrolyte as additives, so that the capacity can be provided by continuous reduction discharge after the positive electrode discharge is finished, and the energy density and the discharge performance of the lithium primary battery can be obviously improved. In order to achieve the purpose, the main technical scheme of the invention is as follows:

a lithium primary battery electrolyte comprises an organic solvent, an additive, other additives and a lithium salt, wherein the additive comprises Li₂S_x、R₁-S-R₂、R₁-S-S-R₂And R₁-S-S-S-R₂Any one or a mixture of two or more of them, wherein x is 2-8, R, R₁And R₂Respectively selected from one of alkyl, alkenyl, alkynyl, aryl, halogenated alkyl, aldehyde group and carboxyl.

Further, the content of the additive accounts for 0.5-50% of the total mass of the lithium primary battery electrolyte in percentage by mass.

Further, the organic solvent includes any one or a mixture of two or more of tetraethylene glycol dimethyl ether, dimethoxyethane, 1, 3-dioxolane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 2-methyltetrahydrofuran, cyclohexane, cyclohexyl ether, tetrahydrofuran, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl butyrate, dimethylene sulfoxide, dimethyl sulfone, methyl ethyl sulfone, and sulfolane.

Further, the lithium salt is selected from lithium hexafluorophosphate (LiPF)₆) Lithium tetrafluoroborate (LiBF)₄) Lithium perchlorate (LiClO)₄) Lithium bis (trifluorosulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium nitrate (LiNO)₃) Lithium aluminum tetrachloride (LiAlCl)₄) And lithium trifluoromethanesulfonate (LiSOCF)₃) Any one or a mixture of two or more of them.

Further, the concentration of the lithium salt in the electrolyte of the lithium primary battery is 0.1-2 mol/L.

Further, the other additive is any one or a mixture of two or more of Vinylene Carbonate (VC), ethylene carbonate (VEC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS), 1,3- (1-Propene) Sultone (PST), Ethylene Sulfite (ES), ethylene sulfate (DTD), dimethyl sulfate (DMS), diethyl sulfate (DES), propylene sulfate (TMS), ethylene sulfite, ethylene carbonate, propylene sulfite, butylene sulfite, dimethyl sulfoxide (DMSO), sulfolane (TMS), Acetonitrile (AN), Succinonitrile (SN), adiponitrile and glutaronitrile.

The invention also provides a preparation method of the electrolyte of the lithium primary battery, which comprises the following steps: under the protection of inert gas, mixing organic solvent, additive, other additives and lithium salt, and uniformly stirring to obtain the lithium primary battery electrolyte.

The invention also provides a lithium primary battery comprising the lithium primary battery electrolyte as described above, preferably, the lithium primary battery is selected from any one of a lithium/graphite fluoride battery, a lithium/manganese dioxide battery and a lithium/ferrous sulfide battery.

Further, the lithium primary battery also comprises a positive electrode, and after the discharge of the positive electrode of the lithium primary battery is completed, the additive in the electrolyte of the lithium primary battery continues to perform reduction discharge to provide capacity.

Compared with the prior art, the invention has the following beneficial effects:

1. the invention adopts inorganic and/or organic polysulfide as the additive of the electrolyte of the lithium primary battery, and can continue to reduce and discharge to provide capacity after the anode discharge is finished, thereby obviously improving the energy density of the lithium primary battery.

2. The preparation method of the lithium primary battery electrolyte provided by the invention is simple to operate, strong in practicability and wide in application range.

[ description of the drawings ]

FIG. 1 is a graph showing a comparison of gram capacities of discharged conventional lithium primary battery electrolytes with those of lithium primary battery electrolytes provided by the present invention, wherein # 1 is a graph showing the gram capacities of discharged conventional lithium primary battery electrolytes used in comparative examples 1-2; and # 2 is a plot of the gram capacities of lithium primary battery electrolytes of the present invention used in examples 4-5.

[ detailed description ] embodiments

The invention aims to provide a lithium primary battery electrolyte, a preparation method thereof and a lithium primary battery using the electrolyte, wherein organic and/or inorganic polysulfide is added into the electrolyte to serve as an additive of the lithium primary battery electrolyte, so that the lithium primary battery can continue to reduce and discharge to provide capacity after positive electrode discharge is finished, and the energy density of the lithium primary battery is remarkably improved, and the main technical scheme of the invention is as follows:

a lithium primary battery electrolyte comprises an organic solvent, an additive, other additives and a lithium salt, wherein the additive comprises Li₂S_x、R₁-S-R₂、R₁-S-S-R₂And R₁-S-S-S-R₂Any one or a mixture of two or more of them, wherein x is 2-8, R, R₁And R₂Respectively selected from one of alkyl, alkenyl, alkynyl, aryl, halogenated alkyl, aldehyde group and carboxyl. In addition, Li₂S_xIs Li₂S_(2-8)I.e. Li₂S_xCan be inorganic lithium polysulfide compound or inorganic lithium polysulfide mixture.

Further, the content of the additive accounts for 0.5-50% of the total mass of the lithium primary battery electrolyte in percentage by mass; preferably, the content of the additive accounts for 0.5-30% of the total mass of the lithium primary battery electrolyte; more preferably, it is 0.5 to 10%.

Further, the organic solvent includes any one or a mixture of two or more of tetraethylene glycol dimethyl ether, dimethoxyethane, 1, 3-dioxolane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 2-methyltetrahydrofuran, cyclohexane, cyclohexyl ether, tetrahydrofuran, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl butyrate, dimethylene sulfoxide, dimethyl sulfone, methyl ethyl sulfone, and sulfolane.

Further, the lithium salt is selected from lithium hexafluorophosphate (LiPF)₆) Lithium tetrafluoroborate (LiBF)₄) Lithium perchlorate (LiClO)₄) Lithium bis (trifluorosulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium nitrate (LiNO)₃) Lithium aluminum tetrachloride (LiAlCl)₄) And lithium trifluoromethanesulfonate (LiSOCF)₃) Any one or a mixture of two or more of them.

Further, the concentration of the lithium salt in the electrolyte of the lithium primary battery is 0.1-2 mol/L.

Further, the other additive is any one or a mixture of two or more of Vinylene Carbonate (VC), ethylene carbonate (VEC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS), 1,3- (1-Propene) Sultone (PST), Ethylene Sulfite (ES), ethylene sulfate (DTD), dimethyl sulfate (DMS), diethyl sulfate (DES), propylene sulfate (TMS), ethylene sulfite, ethylene carbonate, propylene sulfite, butylene sulfite, dimethyl sulfoxide (DMSO), sulfolane (TMS), Acetonitrile (AN), Succinonitrile (SN), adiponitrile and glutaronitrile.

The invention also provides a preparation method of the electrolyte of the lithium primary battery, which comprises the following steps: under the protection of inert gas, mixing organic solvent, additive, other additives and lithium salt, and uniformly stirring to obtain the lithium primary battery electrolyte.

The invention also provides a lithium primary battery, which comprises the lithium primary battery electrolyte, wherein after the discharge of the positive electrode of the lithium primary battery is finished, the additive in the lithium primary battery electrolyte can be continuously reduced and discharged to provide capacity; preferably, the lithium primary battery is selected from any one of a lithium/graphite fluoride battery, a lithium/manganese dioxide battery, and a lithium/ferrous sulfide battery.

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.