Primary lithium battery

Abstract

The present disclosure discloses a primary lithium battery comprising a reactive solid cathode, a liquid electrolyte, a separator, and a lithium anode. The liquid electrolyte is ionic conductive and is configured to undergo a series coupling reaction after solid phase reaction of the reactive solid cathode and the lithium anode. The liquid electrolyte comprises a solvent and an electrolyte salt, and a concentration of the electrolyte salt in the liquid electrolyte is 0.1-3 mol/L. The solvent comprises a sulfite ester type compound and an organic solvent, and a concentration of the sulfite ester type compound in the organic solvent is 5 wt % to 90 wt %.

Claims

1. A primary lithium battery based on a solid-liquid phase series coupling reaction mode comprising: a reactive solid cathode, a liquid electrolyte, a separator, and a lithium anode, wherein: the liquid electrolyte is ionic conductive and is configured to undergo a series coupling reaction after solid phase reaction of the reactive solid cathode and the lithium anode, the liquid electrolyte comprises a solvent and an electrolyte salt, a concentration of the electrolyte salt in the liquid electrolyte is 0.1-3 mol/L, the solvent consists of a sulfite ester type compound and an organic solvent, the organic solvent is at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, butylene carbonate, ethylene glycol dimethyl ether, sulfolane, or dimethyl sulfoxide, a concentration of the sulfite ester type compound in the organic solvent is from 5 wt % to 90 wt %, a reduction potential of the sulfite ester type compound is lower than a reduction potential of the reactive solid cathode, a structural formula of the sulfite ester type compound is as follows: ##STR00004## R is selected from hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group comprising a general formula of —C.sub.xH.sub.2x+1, or an olefin group comprising a general formula of —CH═C.sub.xH.sub.2x, wherein x is an integer selected from 1 to 5, and R′ is selected from hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group comprising a general formula of —C.sub.xH.sub.2x+1, or an olefin group comprising a general formula of —CH═C.sub.xH.sub.2x, wherein x is an integer selected from 1 to 5.

2. The primary lithium battery according to claim 1, wherein the electrolyte salt is at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium hexafluoroarsenate (V), or lithium perchlorate.

3. The primary lithium battery according to claim 1, wherein a material of the reactive solid cathode is selected from metal, non-metal fluoride, or metal oxide.

4. The primary lithium battery according to claim 3, wherein: the non-metal fluoride comprises carbon fluoride, and the metal oxide comprises manganese dioxide.

5. The primary lithium battery according to claim 1, wherein a material of the lithium anode is metallic lithium or an alloy of metallic lithium.

6. The primary lithium battery according to claim 1, wherein the separator is a polymer separator, a composite polymer separator, or an inorganic material separator.

7. The primary lithium battery according to claim 6, wherein: the polymer separator comprises a polypropylene separator or a polyethylene separator, the composite polymer separator comprises a composite polypropylene separator coated with an inorganic modification layer or an organic modification layer, a composite polyethylene separator coated with an inorganic modification layer or an organic modification layer, a composite polypropylene separator uncoated, or a composite polyethylene separator uncoated, and the inorganic material separator comprises a glass fiber separator.

8. A primary lithium battery, comprising: a reactive solid cathode, a liquid electrolyte, a separator, and a lithium anode, wherein: the liquid electrolyte comprises a solvent and an electrolyte salt, a concentration of the electrolyte salt in the liquid electrolyte is 0.1-3 mol/L, the solvent consists of a sulfite ester type compound and an organic solvent, a concentration of the sulfite ester type compound in the organic solvent is 5 wt % to 90 wt %, the organic solvent is at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, butylene carbonate, ethylene glycol dimethyl ether, sulfolane, or dimethyl sulfoxide, a reduction potential of the sulfite ester type compound is lower than a reduction potential of the reactive solid cathode, a structural formula of the sulfite ester type compound is as follows: ##STR00005## R is selected from hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group comprising a general formula of —C.sub.xH.sub.2x+1, or an olefin group comprising a general formula of —CH═C.sub.xH.sub.2x, wherein x is an integer selected from 1 to 5, R′ is selected from hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group comprising a general formula of —C.sub.xH.sub.2x+1, or an olefin group comprising a general formula of —CH═C.sub.xH.sub.2x, wherein x is an integer selected from 1 to 5, and when a voltage of the primary lithium battery is in a range of 3.2 V-2.4 V, an active material of the reactive solid cathode firsts participates in a discharge reaction, and when the voltage of the primary lithium battery drops below 2.4 V, the sulfite ester type compound in the liquid electrolyte also participates in the discharge reaction by acting as a liquid electrode.

9. The primary lithium battery according to claim 8, wherein: the electrolyte salt is at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium hexafluoroarsenate (V), or lithium perchlorate.

10. The primary lithium battery according to claim 8, wherein a material of the reactive solid cathode is selected from metal, non-metal fluoride, or metal oxide.

11. The primary lithium battery according to claim 10, wherein: the non-metal fluoride comprises carbon fluoride, and the metal oxide comprises manganese dioxide.

12. The primary lithium battery according to claim 8, wherein a material of the lithium anode is metallic lithium or an alloy of metallic lithium.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 illustrates a comparative diagram of discharge curves of a lithium-graphite fluoride battery in Embodiment 2 of the present disclosure using a first electrolyte comprising ethylene sulphide (ES) and a second electrolyte not comprising ES, in which a current density is 10 mA/g.

(2) FIG. 2 illustrates a comparative diagram of discharge curves of a lithium-graphene fluoride battery in Embodiment 3 of the present disclosure using a first electrolyte comprising ES and a second electrolyte not comprising ES, in which a current density is 10 mA/g.

(3) FIG. 3 illustrates a comparative diagram of discharge curves of a lithium manganese dioxide battery in Embodiment 4 of the present disclosure using a first electrolyte comprising ES and a second electrolyte not comprising ES, in which a current density is 10 mA/g.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(4) The present disclosure will be further described below with the combination of the accompanying drawings and the embodiments.

(5) In some embodiments, a liquid electrolyte of ethylene sulphide (ES) with a mass percentage (5%-90%) is prepared. The liquid electrolyte is a mixed solution comprising an electrolyte salt, an organic solvent, and the ES. A concentration of the electrolyte salt is 0.1-3 mol/L. The organic solvent is at least one of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), butylene carbonate, ethylene glycol dimethyl ether (DME), sulfolane, or dimethyl sulfoxide. The electrolyte salt is at least one of lithium tetrafluoroborate (LiBF.sub.4), lithium hexafluorophosphate (LiPF.sub.6), lithium hexafluoroarsenate (V) (LiAsF.sub.6), lithium perchlorate (LiClO.sub.4), lithium bis (oxalato) borate (LiBOB), or lithium difluoro (oxalato) borate (LiODFB).

Embodiment 1

(6) Preparing LiPF.sub.6+EC+EMC+ES (x %) (e.g., solution electrolyte) comprising ES with different mass percentages of 1M (1 mol/L) as an electrolyte in a glove box filled with argon gas at room temperature (e.g., 25° C.-50° C.), in which EC:EMC=3:7 (mass ratio). The electrolyte is mixed well.

Comparative Example

(7) Preparing LiPF.sub.6+EC+EMC without ES of 1M (1 mol/L) as an electrolyte in a glove box filled with argon gas at the room temperature, in which EC:EMC=3:7 (mass ratio). The electrolyte is mixed well.

Embodiment 2

(8) Preparing a Lithium-Graphite Fluoride Battery:

(9) Homogenizing a cathode material of graphite fluoride, a conductive agent of acetylene black, and a binder of polyvinylidene fluoride (PVDF) with a ratio of 85:5:10 (mass ratio) at room temperature using a solvent N-methyl-2-pyrrolidone (NMP) to obtain a mixture. Evenly coating the mixture on a copper foam, drying in a vacuum drying oven at 80° C., and pressing into a shape to obtain an electrode of graphite fluoride. In FIG. 1, a first curve 1 illustrates a discharge curve of the graphite fluoride when the electrolyte does not comprise ES, and a second curve 2 illustrates a discharge curve of the graphite fluoride when the electrolyte comprises ES with a mass percentage of 63%. Compared with the electrolyte that does not comprise ES, a specific capacity and a specific energy of a graphite fluoride-ES composite battery system (e.g., in which the electrolyte comprises ES) were respectively increased by 6.5% and 6.7%.

Embodiment 3

(10) Preparing a Lithium-Graphene Fluoride Battery:

(11) Homogenizing a cathode material of graphene fluoride, a conductive agent of acetylene black, and a binder of polyvinylidene fluoride (PVDF) with a ratio of 85:5:10 (mass ratio) at room temperature using a solvent N-methyl-2-pyrrolidone (NMP) to obtain a mixture. Evenly coating the mixture on a copper foam, drying in a vacuum drying oven at 80° C., and pressing into a shape to obtain an electrode of graphene fluoride. In FIG. 2, a first curve 1 illustrates a discharge curve of the graphene fluoride when the electrolyte does not comprise ES, and a second curve 2 illustrates a discharge curve of the graphene fluoride when the electrolyte comprises ES with a mass percentage of 44%. Compared with the electrolyte that does not comprise ES, a specific capacity and a specific energy of a graphene fluoride-ES composite battery system (e.g., in which the electrolyte comprises ES) were respectively increased by 9.9% and 8.5%.

Embodiment 4

(12) Preparing a Lithium-Manganese Dioxide Battery:

(13) Homogenizing a cathode material of manganese dioxide, a conductive agent of acetylene black, and a binder of polyvinylidene fluoride (PVDF) with a ratio of 80:10:10 (mass ratio) at room temperature using a solvent N-methyl-2-pyrrolidone (NMP) to obtain a mixture. Evenly coating the mixture on an aluminum foil, drying in a vacuum drying oven at 80° C., and pressing into a shape to obtain an electrode of manganese dioxide. In FIG. 3, a first curve 1 illustrates a discharge curve of the manganese dioxide when the electrolyte does not comprise ES, and a second curve 2 illustrates a discharge curve of the manganese dioxide when the electrolyte comprises ES with a mass percentage of 44%. Compared with the electrolyte that does not comprise ES, a specific capacity and a specific energy of a manganese dioxide-ES composite battery system (e.g., in which the electrolyte comprises ES) were respectively increased by 62.6% and 45.2%.

Embodiment 5

(14) Using the electrodes prepared in Embodiments 2-4 as a cathode, metallic lithium as an anode, Celgard® 2400 as a separator, and LiPF.sub.6+EC+EMC or LiPF.sub.6+EC+EMC+ES of 1M (1 mol/L) as the electrolyte to assemble 2025 button batteries. Constant current discharge performance tests using a LAND® battery test system (provided by Wuhan Jinnuo Electronics Co., Ltd.), in which a cut-off voltage is 1.5V, a current density is 10 mA/g, a constant temperature of a test environment is 25° C. are performed. Test results are shown in FIGS. 1-3.

(15) A primary lithium battery based on a solid-liquid phase series coupling reaction mode comprises a reactive solid cathode, a liquid electrolyte, a separator, and a lithium anode. The liquid electrolyte is ionic conductive and is configured to undergo a series coupling reaction after solid phase reaction of an electrode (i.e., the reactive solid cathode) and the lithium anode. The liquid electrolyte comprises a solvent and an electrolyte salt. A concentration of the electrolyte salt in the liquid electrolyte is 0.1-3 mol/L. The solvent comprises a sulfite ester type compound and an organic solvent, and a concentration of the sulfite ester type compound in the organic solvent is 5 wt %-90 wt %. A structural formula of the sulfite ester type compound is as follows:

(16) ##STR00003##

(17) R is selected from hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group comprising a general formula of —C.sub.xH.sub.2x+1, or an olefin group comprising a general formula of —CH═C.sub.xH.sub.2x, wherein x is an integer selected from 1-5. R′ is selected from hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group comprising a general formula of —C.sub.xH.sub.2x+1, or an olefin group comprising a general formula of —CH═C.sub.xH.sub.2x, wherein x is an integer selected from 1-5.

(18) A material of the reactive solid cathode is selected from metal, non-metal fluoride, or metal oxide.

(19) A material of the lithium anode is metallic lithium or an alloy of metallic lithium.

(20) The separator is a polymer separator, a composite polymer separator, or an inorganic material separator. Further, the polymer separator comprises a polypropylene separator or a polyethylene separator. The composite polymer separator comprises a composite polypropylene separator coated with an inorganic modification layer or an organic modification layer, a composite polyethylene separator coated with an inorganic modification layer or an organic modification layer, a composite polypropylene separator uncoated, or a composite polyethylene separator uncoated. The inorganic material separator comprises a glass fiber separator.

(21) It will be apparent to those skilled in the art that various modifications and variation can be made in the present disclosure without departing from the spirit or scope of the invention. Thus, it is intended that the present disclosure cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.