Multilayer ceramic solid electrolyte separator with plastic reinforcement for increasing the fracture stability and reducing short circuits in electric batteries

Abstract

A separator for an electric battery includes a first solid electrolyte layer; a plastic separator film impregnated with a liquid or gel electrolyte; and a second solid electrolyte layer, the first and second electrolyte layers sealing the liquid or gel electrolyte in the plastic separator. Also disclosed is a separator where first and second electrolyte layers sealing a plastic separator film and have a porosity less than 5%. A method for manufacturing a separator, an electric battery and a vehicle are also provided.

Claims

1. A method for manufacturing a separator comprising: gluing or laminating a first solid electrolyte layer directly onto a first side of a porous plastic separator having a porosity of 25 to 75%; wetting the porous plastic separator film with a liquid or gel electrolyte after the gluing or laminating the first solid electrolyte layer directly onto the first side of the porous plastic separator; and placing a second solid electrolyte layer onto a second side of the porous plastic separator wetted with the liquid or gel electrolyte.

2. The method as recited in claim 1 wherein the first and second solid electrolyte layers seal the liquid or gel electrolyte in the plastic separator.

3. The method as recited in claim 1 wherein the porous plastic separator is made of a porous polyethylene or polypropylene film.

4. The method as recited in claim 1 wherein the porous plastic separator is a non-lithium ion conducting film.

5. The method as recited in claim 1 wherein the first solid electrolyte layer is made of a material selected from a group consisting of lithium oxide, sulfide glasses, glass ceramics and ceramics.

6. The method as recited in claim 1 wherein the first solid electrolyte layer has a porosity of less than 5%.

7. The method as recited in claim 1 wherein the first solid electrolyte layer is devoid of through-holes.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a prior art battery cell with a ceramic solid electrolyte separator developing a defect;

(2) FIGS. 2a, 2b and 2c show the prior art battery cell of FIG. 1 and the progression of the defect in the battery cell;

(3) FIGS. 3a, 3b, 3c show a prior art battery cell with a conventional plastic film with liquid or gel electrolyte and the progression of a defect in the battery cell;

(4) FIG. 4 shows a schematic of the multi-layer separator of the present invention;

(5) FIG. 5 shows a battery cell of the present invention, with possible defects;

(6) FIG. 6 shows the battery cell of the present invention with a first progression of a defect;

(7) FIG. 7 shows the battery cell of the present invention with a further progression of the defect;

(8) FIG. 8 shows the battery cell of the present invention with a yet further progression of the defect;

(9) FIG. 9 shows the battery cell of the present invention with a still further progression of the defect;

(10) FIG. 10 shows the battery of the present invention with several cells; and

(11) FIG. 11 shows an electric or hybrid vehicle with the battery of the present invention.

DETAILED DESCRIPTION

(12) FIG. 1 shows a prior art lithium-ion battery cell with a copper current collector 10 having a thickness of 8 to 12 micrometers, an anode layer 12 having a thickness of 20 to 40 micrometers, a ceramic solid electrolyte separator 14 having a thickness of 18 to 25 micrometers and a cathode layer 16 having a thickness of 60 to 120 micrometers.

(13) Charging and discharging of the battery cell creates an enormous amount of stress on a surface of the solid electrolyte and the stress increases with the number of surface defects such as small dents, grooves, cracks, or depressions, and with a decrease in temperature. Although lithium is a soft metal, below 60° C. it is does not flow well. When lithium metal accumulates in a depression during charging and fills the space, the next amount of lithium presses the previously deposited lithium away from the solid electrolyte. Depending on the geometry, the situation may arise that the force to move the lithium layer further is not directed away from the solid electrolyte, but instead is directed laterally against it, as shown at depression 18. As a result, the ceramic solid electrolyte can breaks and has a rupture 19, as shown in FIG. 1.

(14) The continuous rupture causes dendrite growth through the separator, and short circuits the cell. This may also result in the rupture developing transversely through the solid electrolyte surface, thus dividing the solid electrolyte into multiple fragments. These fragments are displaced due to vibrations of the vehicle, and the current collector films are cut by sharp-edged fragments.

(15) FIGS. 2a, 2b and 2c show a possible defect progression in a battery cell with a ceramic separator as in FIG. 1, and having an aluminum current collector 20 with a thickness of 12 to 30 micrometers. If the rupture 19 or dendrite grows through the solid electrolyte layer 14 between the anode layer 12 and cathode layer 16, as shown in FIG. 2a, this can short circuit these layers as shown schematically in FIG. 2b. After the short circuit, the dendrite 19 remains in the solid electrolyte layer 14 and at the anode layer 12, even if the lithium were to melt. This melted state shortens local short circuit events enormously, and could even establish a permanent connection between the anode and the cathode. As the result of excessive heating, the cathode material could ignite or be damaged as shown in FIG. 2c at damage area 23, or the lithium in the solid electrolyte could possibly evaporate and cause the solid electrolyte to burst in places.

(16) Conventional plastic separators with electrolyte or gels do not face the exact same problem, but also experience defects. FIGS. 3a, 3b, 3c show a prior art battery cell with a conventional plastic film with liquid or gel electrolyte and the progression of a defect in the battery cell. The conventional battery cell is similar to the cell shown in FIG. 2a, but with a thicker anode layer 112 of 50 to 100 micrometers, and a porous plastic separator 114 of 18 to 25 micrometers having a liquid or gel electrolyte. The dendrite growth in conventional separator 114 is intensified by lower temperatures >0° C. and fast charging >1 C. During charging, the dendrite 119 grows through the plastic separator 114 from the anode layer 112, and contacts the cathode layer 16, resulting in a short circuit. Dendrite 119 has a good connection on the anode layer 112 and a fairly low contact resistance. In comparison, the dendrite 119 end establishing the contact with cathode layer 16 has a higher contact resistance. Since the same current flows through both ends, the different contact resistances result in different rates of heating. There is a greater drop in potential at the high contact resistance, which, multiplied by the short circuit current, results in a greater heating loss and damage to the cathode layer 116 at this location 121, as shown in FIG. 3b. Depending on the size of the dendrite 119 and the magnitude of the charging current, this may result in the dendrite evaporating or melting down, and melting a hole 123 in the separator 114. Polyethylene and/or polypropylene, having a melting temperature of 120° C. to 140° C., are generally used. The porous nature of the plastic separator results in deformations, even below the melting temperature. Cell openings of conventional lithium-ion cells with a porous plastic separator have sometimes exhibited holes having diameters of 0.5 mm to 5 mm in the plastic separator, resulting in poorer performance of the battery cell

(17) FIG. 4 shows a schematic of a preferred embodiment of the multi-layer separator 200 of the present invention. A first solid electrolyte layer 202 of 2 to 15 micrometer thickness, a porous plastic separator film layer 204 of 18 to 25 micrometer thickness impregnated with a liquid or gel electrolyte, and a second solid electrolyte layer 204 of 2 to 15 micrometer thickness.

(18) The first and second electrolyte layers 202, 206 are made of lithium oxide or sulfide glasses or glass ceramics or ceramics, and have a porosity of less than 5%, i.e. from zero to less than 5%. The low porosity layers 202, 206 thus do not have through-holes, and seal the gel or liquid electrolyte in the porous plastic separator film layer 204. The porous plastic separator film layer 204 can have a porosity of for example in a range of 25 to 75%, and more preferably from 30 to 60%.

(19) Mechanical reinforcement of the thin solid electrolyte layers 202, 204, which are for example made of ceramic, with a porous/perforated plastic film 204 increases the rupture strength and prevents displacement of possible sharp-edged fragments in the event that a rupture occurs. Without the reinforcement film 204, the surface of the solid electrolyte 202, 204 must be virtually perfect.

(20) First solid electrolyte layer 202 can have a layer thickness 0.5 μm to 50 μm, and can aid in separation of the cathode side from the metallic lithium anode or plated metallic lithium from a carbon/graphite based anode. Metallic lithium is very reactive, and reacts with the components of the liquid/gel electrolyte; the reaction speed and the resulting heat of reaction increase dramatically during a short circuit and heating of the cell. Conventional lithium-ion batteries containing liquid electrolytes and metallic lithium have often ignited or even exploded in laptops, due to dendrites. The first solid electrolyte layer 202 can aid in preventing such issues, and the use of metallic lithium is an advantage of the present invention. However, intercalated lithium also can be used as an anode in less preferred embodiments.

(21) Porous plastic separator layer 204 can help provide mechanical reinforcement of the first solid electrolyte layer 202, and increases the rupture strength and fixes possible fragments of the solid electrolyte layer 202 to the separator layer 204.

(22) For lithium-ion conductivity, plastic separator 204 itself preferably is not lithium ion conductive but rather preferably is impregnated with a liquid/gel electrolyte. A gelled liquid electrolyte is preferably used, which on the one hand has the task of transporting the lithium ions through the plastic separator 204, and on the other hand cushions the mechanical stress on the second solid electrolyte 204.

(23) However, in some less preferable embodiments, a plastic separator 204 made for example of lithium-ion conductive plastic material such as PEO can be used.

(24) Second solid electrolyte layer 206 can be similar to the first electrolyte layer 202, and also can be thinner, for example from thicknesses ranging from 0.5 μm to 20 μm and made of ceramic.

(25) FIG. 5 shows a battery cell of the present invention, with possible defects 218, 219.

(26) The battery cell has a current collector 10, for example a copper foil of 8 to 12 micrometer thickness, and anode layer 212 of for example pure metallic lithium with a preferred thickness of 20 to 40 micrometers, separator 200 as described in FIG. 4, a cathode layer 16 with a preferred thickness of 60 to 120 micrometers and made for example of lithium metal oxides such as lithium nickel-manganese-cobalt oxide (“NMC”) mixed with a binder and electric conductive material, and a current collector 20 made for example of aluminum foil with a thickness of 12 to 30 micrometers. The battery cell defines an SPGS unit.

(27) The multilayer structure assists the SPGS unit in dealing with defects, as shown in FIGS. 6, 7, 8 and 9.

(28) As shown in FIG. 6, a dendrite 221 may grow from defect 218 in first solid electrolyte layer 202 through the plastic separator layer 204. However, any defect 219 in solid electrolyte layer 206 is not likely to be at the exact same location, and thus the dendrite 221 is blocked at layer 206.

(29) As use of the battery cell continues, lithium can pass through dendrite 221, but will collect on the nonporous second electrolyte layer 206 due to the sealing function of the second electrolyte layer 206, as shown in FIG. 7.

(30) Even if the lithium reaches defect 219 in second electrolyte layer 206, and a short circuit results at 224, the SPGS unit can still function, albeit with some reduced functionality, since the plastic separator material will melt as shown in FIG. 9 and form a hole 226. Hole 226 in the plastic separator 204 also reduces the likelihood that a dendrite connection will form once again at this location. Dendrite growth is retarded at this location as dendrite growth competes with the dendrite degradation during discharging. The dendrite degradation is accelerated during slow discharging (<0.5 C) and at temperatures above 0° C.

(31) Second solid electrolyte 206 and the SPGS unit construction thus reduces the likelihood of a short circuit event enormously due to stochastic distribution of surface defects. For the first solid electrolyte 202, a metallic lithium film forms on the entire surface of the solid electrolyte; i.e., all open pores, grooves, notches, depressions, dents, and gaps are necessarily filled with lithium. If these defects have an unfavorable size and geometry, crack formation occurs. However, the further plastic separator 204 and second solid electrolyte layer 206 reduce the negative effects of such crack formation.

(32) FIG. 10 shows a further embodiment of a separator 30 in which SPGS units may be further combined into multilayer units to form a SPGS unit composite of several plastic separator layers 304, 404, 504 similar to layer 204. Solid electrolyte layers 302, 306, 406, 506 may be similar to layers 202 and 206 and have for example a thickness of 2 to 15 micrometers.

(33) In the embodiments above, for quick processing, the dry plastic separator is glued or laminated onto a rear side of a solid electrolyte layer. The plastic separator can then be wetted with gel or liquid to form layers 204, 304, 404, 504, and the next solid electrolyte later added to seal the gel or liquid.

(34) As shown schematically in FIG. 11, in one application, the battery cells can be formed used in a battery 1000 providing power as an electric battery to an electric motor 1001 for powering an electric or hybrid vehicle 1002.