Glass-fiber containing composite materials for alkali metal-based batteries and methods of making

Abstract

Glass-fiber composites are described that include a substrate containing glass fibers and particles in contact with the glass fiber substrate. The particles may include an alkali-metal containing compound. In addition, batteries are described with an anode, a cathode, and an electrolyte. The cathode may include alkali-metal containing nanoparticles in contact with glass fibers. Also describe are methods of making a glass-fiber composite. The methods may include the steps of forming a wet laid non-woven glass fiber substrate, and contacting alkali-metal containing particles on the substrate.

Claims

1. A method of making a glass-fiber composite, the method comprising the steps of: forming a wet laid non-woven glass fiber substrate, wherein the glass fiber substrate comprises a sodium-based compound selected from the group consisting of NaMnO.sub.2; NaNiO.sub.2; Na(Ni.sub.0.5Mn.sub.0.5)O.sub.2, NaFePO.sub.4, Na.sub.2Fe.sub.2(SO.sub.4).sub.3, and Na.sub.2Mn.sup.11[Mn.sup.11(CN).sub.6]; and contacting alkali-metal containing particles on the substrate.

2. The method of claim 1, wherein the contacting of the alkali-metal containing particles on the substrate comprises coating, embedding, or saturating the substrate with the particles.

3. The method of claim 1, wherein the sodium-based compound is selected from the group consisting of NaNiO.sub.2, Na(Ni.sub.0.5Mn.sub.0.5)O.sub.2, NaFePO.sub.4, Na.sub.2Fe.sub.2(SO.sub.4).sub.3, and Na.sub.2Mn.sup.II[Mn.sup.II(CN).sub.6].

4. A glass fiber substrate comprising glass fibers that comprise a sodium-based compound selected from the group consisting of NaNiO.sub.2, Na(Ni.sub.0.5Mn.sub.0.5)O.sub.2, NaFePO.sub.4, Na.sub.2Fe.sub.2(SO.sub.4).sub.3, and Na.sub.2Mn.sup.II[Mn.sup.II(CN).sub.6].

5. The glass fiber substrate of claim 4, wherein the glass fibers comprise nanofibers.

6. A glass-fiber composite comprising: a substrate comprising glass fibers, wherein the glass fibers comprise a sodium-based compound selected from the group consisting of NaMnO.sub.2, NaNiO.sub.2, Na(Ni.sub.0.5Mn.sub.0.5)O.sub.2, NaFePO.sub.4, Na.sub.2Fe.sub.2(SO.sub.4).sub.3, and Na.sub.2Mn.sup.II[Mn.sup.II(CN).sub.6]; and particles in contact with the substrate, wherein the particles comprise an alkali-metal containing compound.

7. The composite of claim 1, wherein the glass fibers comprise non-woven glass microfibers.

8. The composite of claim 1, wherein the alkali-metal containing compound comprises a lithium-containing compound or a sodium-containing compound.

9. The composite of claim 1, wherein the alkali-metal containing compound comprises LiFePO.sub.4.

10. The composite of claim 6, wherein the composite comprises a cathode of a battery.

11. The composite of claim 1, wherein the sodium-based compound is selected from the group consisting of NaNiO.sub.2, Na(Ni.sub.0.5Mn.sub.0.5)O.sub.2, NaFePO.sub.4, Na.sub.2Fe.sub.2(SO.sub.4).sub.3, and Na.sub.2Mn.sup.II[Mn.sup.II(CN).sub.6].

12. The composite of claim 1, wherein the substrate has a surface area ranging from about 20 m.sup.2/g to about 300 m.sup.2/g.

13. The composite of claim 1, wherein: the glass-fiber composite is formed by coating, embedding, or saturating the substrate with the particles, and the particles comprise nanoparticles.

14. The composite of claim 13, wherein the glass-fiber composite is formed by embedding the substrate with the particles.

15. A battery comprising: an anode; a cathode that includes glass fibers comprising a sodium-based compound selected from the group consisting of NaMnO.sub.2, NaNiO.sub.2, Na(Ni.sub.0.5Mn.sub.0.5)O.sub.2, NaFePO.sub.4, Na.sub.2Fe.sub.2(SO.sub.4).sub.3, and Na.sub.2Mn.sup.II[Mn.sup.II(CN).sub.6]; an electrolyte; and a separator.

16. The battery of claim 15, wherein the cathode comprises lithium-containing nanoparticles in contact with the glass fibers.

17. The battery of claim 15, wherein the cathode comprises sodium-containing nanoparticles in contact with the glass fibers.

18. The battery of claim 15, wherein the electrolyte comprises LiPF.sub.6.

19. The battery of claim 15, wherein the glass fibers comprise glass nanofibers.

20. The battery of claim 15, wherein the sodium-based compound is selected from the group consisting of NaNiO.sub.2, Na(Ni.sub.0.5Mn.sub.0.5)O.sub.2, NaFePO.sub.4, Na.sub.2Fe.sub.2(SO.sub.4).sub.3, and Na.sub.2Mn.sup.II[Mn.sup.II(CN).sub.6].

21. The battery of claim 15, wherein the separator comprises a porous membrane.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Glass fiber composites are described that may be used as electrodes in electrical storage batteries, among other devices and applications. Examples of the composites include non-woven glass microfibers that provide a durable, dimensionally stable, microporous substrate for alkali-metal containing nanoparticles, such as lithium and/or sodium-containing nanoparticles. Specific examples of these nanoparticles may include lithium iron phosphate (LiFePO.sub.4), sodium iron fluorophosphate (Na.sub.2FePO.sub.4F) nanoparticles, and other sodium-containing nanoparticles described herein.

(2) Also described are glass fiber substrates made from glass fibers that incorporate sodium iron fluorophosphates. Making the glass fibers out of Na.sub.2FePO.sub.4F may obviate the need to introduce nanoparticles to the fibers when forming an electrode. These fibers may have micro- and/or nano-sized diameters that are similar or the same as the scale of the nanoparticles.

(3) Glass fiber substrates may include a sodium compound. A sodium compound may include a sodium metal oxide, a sodium phosphate, a sodium sulfate, a sodium cyanide, or a derivative thereof, or a mixture thereof. The metal in the sodium metal oxide may be a transition metal. The metal in the sodium metal oxide may include two different metal atoms. The metal in the sodium compound may have an oxidation state of +2. Examples of a sodium compound may include NaMnO.sub.2, NaNiO.sub.2, Na(Ni.sub.0.5Mn.sub.0.5)O.sub.2, NaFePO.sub.4, Na.sub.2Fe.sub.2(SO.sub.4).sub.3, and Na.sub.2Mn.sup.II[Mn.sup.II(CN).sub.6]. The glass fiber substrate may exclude any compound or group of compounds described herein.

(4) The composites may be made by combining a wet laid non-woven gas-fiber substrate with the nanoparticles. The nanoparticles may be introduced to the substrate by among other methods, coating, embedding, or saturating the nanoparticles in the substrate. Nanoparticles may include sodium compounds. The nanoparticles may include a sodium metal oxide, a sodium phosphate, a sodium sulfate, a sodium cyanide, a derivative thereof, or a mixture thereof. The metal in the sodium metal oxide may be a transition metal. The metal in the sodium metal oxide may include two different metal atoms. The metal in the sodium compound may have an oxidation state of +2. Examples of a sodium compound may include NaMnO.sub.2, NaNiO.sub.2, Na(Ni.sub.0.5Mn.sub.0.5)O.sub.2, NaFePO.sub.4, Na.sub.2Fe.sub.2(SO.sub.4).sub.3, and Na.sub.2Mn.sup.II[Mn.sup.II(CN).sub.6]. The nanoparticle may exclude any compound or group of compounds described herein.

(5) Both the above-described materials may be formed into a cathode electrode of an electrical storage battery. The cathode may be separated from the anode electrode by an electrolyte. The electrolyte may be, for example, a micro-porous separator membrane that contains LiPF.sub.6, and the anode electrode may be a metallic anode such as a lithium metal anode or an alloy of two or more metals.

(6) Structural cathodes made from the composite materials have increased surface area for holding the nanoparticles, and may be incorporated into larger, more reliable cells having reduced winding costs. The high-surface area glass fiber substrates may include substrates with surface areas ranging from about 20 m.sup.2/g to about 300 m.sup.2/g or more.

(7) Increasing the accessible surface area of the cathode can increase the ion mass transfer through the cathode as well as the total energy density of the cathode and battery. The present cathodes may include hierarchically porous structures that combine micro- and nanoscale pores to increase the structural integrity and surface area of the cathode material. Batteries that include the present cathodes may achieve power outputs of 760 W/kg or more, and energy densities of about 100 mAh/g or more. The batteries can also have improved cycle performance with losses of about 3% or less over about 700 cycles.

(8) The composite materials have high-surface area produced by forming the glass mircofibers and/or nanofibers into strong, durable, non-woven mats. The fiberglass mats may be fashioned into a micro- and/or nanoporous substrate. They may provide improved mechanical and thermal properties, as well as improved dimensional stability during electrical charging and discharging. This can increase the overall life span of batteries made with these materials. The increased strength of these composite materials also allows more rapid winding of cells and can increase the size of the cells, both of which can lower manufacturing costs of the batteries.

(9) Batteries made with the present glass fiber materials (either with or without nanoparticles) may have a number of advantages over current lithium-ion battery technology. These advantages may include:

(10) Specific Energy Density (Wh/kg)The present batteries can meet or exceed about 200 Wh/kg (system) and about 400 Wh/kg (cell).

(11) Volumetric Energy Density (Wh/l)The increased strength provided by the glass fiber substrate allow tighter packing of the battery electrodes and separator. The nanoporous electrodes allow the electrolyte to penetrate into the electrodes, thus creating an efficient utilization of space. Sodium glass (e.g., Na.sub.2FePO.sub.4F) cathodes may have a lower intrinsic power density than cathodes using lithium-containing nanoparticles, but because active areas of the sodium glass cathodes include the fibers themselves, there is less inactive area for these cathodes.

(12) System Cost (kWh/$)For sodium glass cathodes, cost reductions may be realized due to the decreased use of lithium. These cathodes can reduce costs to about US$250/kWh or less. For cathodes that include Li-containing nanoparticles cost reductions of about 20% to about 40% compared to conventional Li-ion batteries may be realized from the reduction in cell windings and increased cell size.

(13) Specific Power Density (W/kg)Nanoscale systems can increase power density at high discharge rates owing to their increased ion mass transfer. The present batteries may have power densities of about 760 W/kg and energy density of about 100 mAh/g. The present materials may also be incorporated into system features such as ultracapacitors that can boost power in pulses.

(14) Volumetric Power Density (WA)Cathodes made from the present materials can have improved high-drain performance.

(15) Cycle Life (#)Batteries may achieve about 1000 or more cycles. Binding materials and techniques are employed to reduce the unbinding of nanoparticles from the glass-fiber substrate in those embodiments where nanoparticles are used. For sodium-glass cathodes that do not have bound nanoparticles, even larger numbers of cycles may be achieved.

(16) Round Trip EfficiencyThe present batteries may have discharge capacity losses of about 3% or less over 700 cycles at a rate of 1.5 C. At C/3, the capacity loss may be significantly lower.

(17) Temperature ToleranceThe present composites, substrates, cathodes, and batteries may have maximum operating temperatures of about 65 C. or more.

(18) Self DischargeThe present materials may be optimized to reduce the self discharge rate to what is comparable in conventional Li-ion batteries.

(19) SafetyThe present materials include phosphate containing active electrode materials. Phosphates (PO.sub.4) typically have more tightly bound oxygen groups than other conventional electrode materials (e.g., LiCoO.sub.2). This reduces the risk of oxygen liberation that can contribute to fires and explosions in the phosphate-containing batteries and systems. The strength and stability of the glass-fiber substrate can also reduce the incidents of short circuits in the battery and other catastrophic failure modes.

(20) Calendar Life (Years)The glass fiber substrates do not interfere with battery operation and iron-phosphate systems have significantly lower degradation rates than conventional Li-ion batteries and systems. The present batteries may have an increased lifetime compared to the average lifetime for a conventional system.

(21) Having described several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the invention. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present invention. Accordingly, the above description should not be taken as limiting the scope of the invention.

(22) Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

(23) As used herein and in the appended claims, the singular forms a, an, and the include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a process includes a plurality of such processes and reference to the electrode includes reference to one or more electrodes and equivalents thereof known to those skilled in the art, and so forth.

(24) Also, the words comprise, comprising, include, including, and includes when used in this specification and in the following claims are intended to specify the presence of stated features, integers, components, or steps, but they do not preclude the presence or addition of one or more other features, integers, components, steps, acts, or groups.