Primary lithium battery having a DME-free electrolyte

Abstract

A DME-free lithium battery includes a positive electrode, a negative electrode, a separator arranged between the positive electrode and the negative electrode, and a liquid electrolyte composed of a solvent and at least one lithium electrolyte salt and with which the electrode and the separator are impregnated, wherein the solvent includes propylene carbonate (PC) as a first solvent component and 1,3-dioxolane (DOL) as a second solvent component, and the positive electrode and/or the negative electrode have a proportion of carbon black having a BET surface area of at least 1 m.sup.2/g.

Claims

1. A DME-free lithium battery comprising: a positive electrode, a negative electrode, a separator arranged between the positive electrode and the negative electrode, and a liquid electrolyte composed of a solvent and at least one lithium electrolyte salt comprising lithium perchlorate (LiClO.sub.4) present in the electrolyte in a concentration of 5% by weight to 17% by weight, and with which the electrode and the separator are impregnated, wherein the solvent comprises 30-60% by volume propylene carbonate (PC) as a first solvent component and 40-70% by volume 1,3-dioxolane (DOL) as a second solvent component, and the positive electrode and/or the negative electrode have a proportion of carbon black 1) having a BET surface area of 1 m.sup.2/g to 30 m.sup.2/g and 2) of 2 to 10% by weight, based on the dry weight of solid constituents of the positive and/or negative electrode.

2. The battery according to claim 1, wherein the positive electrode comprises manganese dioxide as an active material, and the negative electrode comprises metallic lithium as an active material.

3. A DME-free lithium battery comprising: a positive electrode, a negative electrode, a separator arranged between the positive electrode and the negative electrode, and a liquid electrolyte composed of a solvent and at least one lithium electrolyte salt comprising lithium perchlorate (LiClO.sub.4) present in the electrolyte in a concentration of 5% by weight to 17% by weight, and with which the electrode and the separator are impregnated, wherein the solvent comprises 10-60% by volume propylene carbonate (PC) as a first solvent component, 50-70% by volume 1,3-dioxolane (DOL) as a second solvent component, and 0-50% by volume ethylene carbonate (EC) as a third solvent component, and the positive electrode and/or the negative electrode have a proportion of carbon black 1) having a BET surface area of 1 m.sup.2/g to 30 m.sup.2/g and 2) of 2 to 10% by weight, based on the dry weight of solid constituents of the positive and/or negative electrode.

4. The battery according to claim 3, wherein the positive electrode comprises manganese dioxide as an active material, and the negative electrode comprises metallic lithium as an active material.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 is a graph of battery discharge curves.

DETAILED DESCRIPTION

(2) It will be appreciated that the following description is intended to refer to specific examples selected for illustration in the drawing and is not intended to define or limit the disclosure, other than in the appended claims.

(3) Our lithium batteries comprise, like known lithium batteries, a positive electrode, a negative electrode, a separator arranged between the positive electrode and the negative electrode and a liquid electrolyte composed of a solvent and at least one lithium electrolyte salt and with which the electrode and the separator are impregnated.

(4) The lithium battery is a primary battery, i.e., a battery not intended to be recharged.

(5) The battery is preferably a single cell having precisely one positive electrode and one negative electrode.

(6) In contrast to most known lithium batteries, our batteries are free of DME. More specifically, they have an electrolyte free of DME.

(7) The solvent of the electrolyte comprises PC as a first solvent component and 1,3-dioxolane (DOL) as a second solvent component. Preferably, the solvent of the electrolyte can consist of these two components.

(8) The positive electrode and/or the negative electrode have a proportion of carbon black having a BET surface area of at least 1 m.sup.2/g as determined in accordance with DIN ISO 9277. The carbon black particularly preferably has a BET surface area of 1 m.sup.2/g to 30 m.sup.2/g as determined in accordance with DIN ISO 9277.

(9) The positive electrode and/or the negative electrode preferably contain the carbon black in a proportion of 2 to 10% by weight, preferably 2 to 5% by weight (based on the dry weight of the solid constituents of the electrode). In general, the dry weight of the electrode is made of the weight of the proportion of carbon black and an active material and also, optionally, a binder.

(10) In first experiments, the replacement of DME by DOL resulted in a capacity decrease, even though this was smaller than when using the further second solvent components mentioned at the outset. However, this capacity decrease could surprisingly significantly be reduced by using carbon black having the abovementioned BET values.

(11) Preferably, the solvent comprises the PC in a proportion of 30% by volume to 60% by volume and the DOL in a proportion of 40% by volume to 70% by volume.

(12) Particularly preferably, the proportions of PC and of DOL in the solvent can add up to 100% by volume.

(13) Further preferably, the solvent can comprise ethylene carbonate (EC) as a third solvent component in addition to the PC and the DOL.

(14) We found that the capacity values of our batteries can be improved even further by addition of EC.

(15) In these examples, the solvent preferably comprises PC in a proportion of 10% by volume to 60% by volume and DOL in a proportion of 40% by volume to 70% by volume and EC in a proportion of 0% by volume to 50% by volume.

(16) Particularly preferably, the proportions of PC, DOL and EC in the solvent can add up to 100% by volume.

(17) As the at least one lithium electrolyte salt, the electrolyte particularly preferably comprises lithium perchlorate (LiClO.sub.4). The electrolyte salt, in particular the LiClO.sub.4, is preferably present in the electrolyte in a concentration of 5% by weight to 17% by weight based on the total weight of the liquid electrolyte which preferably composed of the above discussed solvent and the at least one lithium electrolyte salt.

(18) It can be preferred that the electrolyte of our battery comprises additives. Known examples are propane sultone or vinylene carbonate that can have a stabilizing effect on the electrolytes of lithium ion batteries.

(19) Additives can be present in the electrolyte in a proportion of up to 10% by weight, preferably up to 5% by weight based on the total weight of the liquid electrolyte which is preferably composed of the above discussed solvent and the at least one lithium electrolyte salt and the additives.

(20) Particularly preferably, the positive electrode comprises manganese dioxide as an active material.

(21) The negative electrode of the battery preferably comprises metallic lithium as an active material.

(22) Preferably, the positive electrode and/or the negative electrode contain an electrode binder. This can be, for example, carboxymethylcellulose or a carboxymethylcellulose derivative.

(23) As a separator, our batteries can have, for example, a polyolefin separator.

(24) The features described and also further features of our batteries can be derived from the following description of a preferred example. The example described serves merely for the purpose of illustration and to give a better understanding and are not to be construed as constituting any restriction.

(25) (1) Our Cells

(26) Test cells having a negative electrode composed of metallic lithium and a positive electrode composed of manganese dioxide were impregnated with a DME-free electrolyte composed of a solvent and an electrolyte salt. The solvent consisted of the following components: 43% by volume of PC 57% by volume of DOL.
LiClO.sub.4 was used as electrolyte salt. This was added to the solvent in a concentration of 10% by weight.

(27) The positive electrode comprised a proportion of carbon black of 3% by weight in addition to the manganese dioxide. The carbon black had a BET surface area of 2 m.sup.2/g as determined in accordance with DIN ISO 9277.

(28) (2) Reference Cells

(29) Reference cells were manufactured with identical parameters. In the production of the electrolyte, the classical DME was used instead of DOL. The solvent consisted of the following components: 59% by weight of PC 31.2% by weight of DME.
LiClO.sub.4 was used as electrolyte salt. This was added to the solvent in a concentration of 9.8% by weight.

(30) The positive electrode comprised a proportion of carbon black of 3% by weight in addition to the manganese dioxide. The carbon black had a BET value of 0.6.

(31) (3) Comparative Studies

(32) In the case of discharge with a resistance of 620, our test cells attained capacity values of 837 to 885 mAh. The measured capacity values for the reference cells were 830 to 857 mAh.

(33) When other commercial solvents, e.g., EMC or GBL, are used instead of DME, we found that significantly lower capacity values are achieved under identical discharge conditions.

(34) The discharge curves of our cell (continuous and dotted line) and a reference cell (broken line) are shown in FIG. 1.

(35) Although the our batteries have been described in connection with specific forms thereof, it will be appreciated that a wide variety of equivalents may be substituted for the specified elements described herein without departing from the spirit and scope of this disclosure as described in the appended claims.