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Partially and fully surface-enabled alkali metal ion-exchanging energy storage devices

a metal ion-exchanging battery and partially surface-enabled technology, applied in the direction of positive electrodes, electrochemical generators, cell components, etc., can solve the problems of reducing the power density of conventional supercapacitors (symmetric and asymmetric) and limiting the chemical reaction, so as to eliminate the potential formation of dendrites and uniform electric fields

Active Publication Date: 2017-07-06
GLOBAL GRAPHENE GRP INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0047]To illustrate the operational principle of a fully surface-enabled, alkali ion-exchanging battery device (FIG. 4(A)), one may consider a case wherein an alkali source (e.g. small pieces of sodium foil or powder) is implemented between a nano-structured anode (e.g. composed of functionalized graphene sheets) and a porous polymer separator when the battery device is made, and wherein a nano-structured cathode comprises functionalized graphene sheets surrounded by interconnected pores that are preferably meso-scaled (2 nm-50 nm), but can be smaller than 2 nm. Referring to FIG. 4(A)-(C), during the first discharge cycle, alkali foil is ionized to generate alkali ions in the liquid electrolyte. Alkali ions rapidly migrate through the pores of the polymer separator into the cathode side. Since the cathode is also meso-porous having interconnected pores to accommodate liquid electrolyte therein, alkali ions basically just have to sail through liquid to reach a functional group on a surface or edge of a graphene sheet at the cathode. The subsequent surface redox reaction between an alkali ion and a surface-borne functional group (e.g., carbonyl, >C═O illustrated in FIG. 5(C)) is fast and reversible. Because all the steps (alkali ionization, liquid phase diffusion, and surface redox reaction) are fast and no solid-state diffusion is required, the whole process is very fast, enabling fast discharging and a high power density. This is in stark contrast to the conventional lithium-ion battery or sodium-ion battery wherein lithium or sodium ions are required to diffuse into the bulk of a solid cathode particle (e.g., micron-sized lithium cobalt oxide or Na4Mn9O18 particles at the cathode), which is a very slow process.
[0052]In addition, the uniform dispersion of these surfaces of a nano material (e.g. graphene or CNT) in an electrode also provides a more uniform electric field in the electrode in which metal ions / atoms can more uniformly deposit without forming a dendrite. More surface areas also mean more deposition spots and each spot only has a small quantity of metal atoms, insufficient to form a dangerous dendrite. Such a nano-structure eliminates the potential formation of dendrites, which was the most serious problem in conventional lithium metal batteries.

Problems solved by technology

They are chemical reaction-limited, extremely slow, and exhibiting power densities even lower than those of conventional lithium-ion cells.
The conventional supercapacitors (both symmetric and asymmetric) do not meet this requirement since no ion exchange occurs between the two electrodes.

Method used

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  • Partially and fully surface-enabled alkali metal ion-exchanging energy storage devices
  • Partially and fully surface-enabled alkali metal ion-exchanging energy storage devices
  • Partially and fully surface-enabled alkali metal ion-exchanging energy storage devices

Examples

Experimental program
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Effect test

example 1

NGPs from Sulfuric Acid Intercalation and Exfoliation of MCMBs

[0170]MCMB 2528 microbeads (Osaka Gas Chemical Company, Japan) have a density of about 2.24 g / cm3; a median size of about 22.5 microns, and an inter-planar distance of about 0.336 nm. MCMB 2528 (10 grams) were intercalated with an acid solution (sulfuric acid, nitric acid, and potassium permanganate at a ratio of 4:1:0.05) for 24 hours. Upon completion of the reaction, the mixture was poured into deionized water and filtered. The intercalated MCMBs were repeatedly washed in a 5% solution of HCl to remove most of the sulphate ions. The sample was then washed repeatedly with deionized water until the pH of the filtrate was neutral. The slurry was dried and stored in a vacuum oven at 60° C. for 24 hours. The dried powder sample was placed in a quartz tube and inserted into a horizontal tube furnace pre-set at a desired temperature, 600° C. for 30 seconds to obtain exfoliated graphite. The exfoliated MCMB sample was subjected...

example 2

Preparation of Nano-Structured, Functionalized Soft Carbon (One Type of Disordered Carbon)

[0172]Functionalized soft carbon was prepared from a liquid crystalline aromatic resin. The resin was ground with a mortar, and calcined at 900° C. for 2 h in a N2 atmosphere to prepare the graphitizable carbon or soft carbon. The resulting soft carbon was mixed with small tablets of KOH (four-fold weight) in an alumina melting pot. Subsequently, the soft carbon containing KOH was heated at 750° C. for 2 h in N2. Upon cooling, the alkali-rich residual carbon was washed with hot water until the outlet water reached a pH value of 5-7. The activated soft carbon (porous and nano-structured) was then immersed in a 90% H2O2-10% H2O solution at 45° C. for an oxidation treatment that lasted for 2 hours. Then, the resulting partially oxidized soft carbon was immersed in HCOOH at room temperature for functionalization for 24 hours. The resulting porous, functionalized soft carbon was dried by heating at ...

example 3

Nano-Structured Soft Carbon-Based Surface-Enabled Alkali Battery Devices

[0173]Fully surface-enabled coin cells using functionalized soft carbon as a cathode and functionalized soft carbon as a nano-structured anode (plus a small piece of potassium foil as a potassium source implemented between a current collector and a separator layer, Sample-1A) were made and tested. The separator was one sheet of micro-porous membrane (Celgard 2500). The current collector for each of the two electrodes was a piece of carbon-coated aluminum foil. The nano-structured electrode was a porous composite composed of 85 wt. % functionalized soft carbon (+5% Super-P and 10% PTFE binder coated on Al foil). The electrolyte solution was 1 M KPF6 dissolved in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) with a 3:7 volume ratio. The separator was wetted by a minimal amount of electrolyte to reduce the background current. Cyclic voltammetry and galvanostatic charge-discharge measurements of ...

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Abstract

A surface-enabled, metal ion-exchanging battery device comprising a cathode, an anode, a porous separator, and a metal ion-containing electrolyte, wherein the metal ion is selected from (A) non-Li alkali metals; (B) alkaline-earth metals; (C) transition metals; (D) other metals such as aluminum (Al); or (E) a combination thereof; and wherein at least one of the electrodes contains therein a metal ion source prior to the first charge or discharge cycle of the device and at least the cathode comprises a functional material or nano-structured material having a metal ion-capturing functional group or metal ion-storing surface in direct contact with said electrolyte, and wherein the operation of the battery device does not involve the introduction of oxygen from outside the device and does not involve the formation of a metal oxide, metal sulfide, metal selenide, metal telluride, metal hydroxide, or metal-halogen compound. This energy storage device has a power density significantly higher than that of a lithium-ion battery and an energy density dramatically higher than that of a supercapacitor.

Description

[0001]This application is a divisional of U.S. patent application Ser. No. 12 / 930,294 (Jan. 3, 2001).[0002]This is a co-pending application of A. Zhamu, et al “Surface-Controlled, Lithium Ion-Exchanging Energy Storage Device,” US Patent Application Submitted on Dec. 22, 2010.[0003]This invention is based on the research results of a project sponsored by the US National Science Foundation SBIR-STTR Program.FIELD OF THE INVENTION[0004]The present invention relates generally to the field of electrochemical energy storage devices and, more particularly, to a totally new metal ion-exchanging battery device wherein the operation of either the cathode or both the anode and the cathode is intercalation-free (i.e. does not involve metal ion diffusion in and out of the bulk of a solid electrode-active material). The metal ions are exchanged between an anode active material and a cathode active material during charge or discharge cycles. The metal ion storage mechanism in either the cathode or...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): H01M10/0569H01M4/60H01M10/0565
CPCH01M10/0569H01M2004/028H01M4/606H01M10/0565H01M4/13H01M4/366H01M4/622H01M4/625H01M10/054H01M10/0568H01M2300/0028Y02E60/10
Inventor ZHAMU, ARUNAJANG, BOR Z.
Owner GLOBAL GRAPHENE GRP INC
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