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Production method for electrochemically stable anode particulates for lithium secondary batteries

a production method and anode technology, applied in the manufacture of final products, cell components, electrochemical generators, etc., can solve the problems of dramatically increasing charge/discharge cycle numbers and reducing the decay rate of battery capacity

Active Publication Date: 2020-04-16
GLOBAL GRAPHENE GRP INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The patent text describes a method for improving the performance of lithium batteries. The method involves using a thin layer of particulate material made of graphene sheets, which are placed between the anode and the electrolyte of the battery. This layer of particulate helps to accommodate the volume expansion of the anode material during charging, while also reducing the formation and destruction of a solid-electrolyte interface (SEI) phase. By controlling the volume expansion of the particulate, the battery has a longer life and can charge and discharge more times without losing capacity. The method also involves operating the battery in a way that prevents the anode from being at a high electrochemical potential during the initial charge cycles. This results in a more stable surface for the battery and further improves its performance.

Problems solved by technology

We have discovered that this strategy surprisingly results in significantly reduced battery capacity decay rate and dramatically increased charge / discharge cycle numbers.

Method used

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  • Production method for electrochemically stable anode particulates for lithium secondary batteries
  • Production method for electrochemically stable anode particulates for lithium secondary batteries
  • Production method for electrochemically stable anode particulates for lithium secondary batteries

Examples

Experimental program
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Effect test

example 1

Graphene Oxide from Sulfuric Acid Intercalation and Exfoliation of MCMBs and Production of Graphene / Carbon-Encapsulated Particles

[0147]MCMB (mesocarbon microbeads) were supplied by China Steel Chemical Co. This material has a density of about 2.24 g / cm3 with a median particle size of about 16 μm. MCMBs (10 grams) were intercalated with an acid solution (sulfuric acid, nitric acid, and potassium permanganate at a ratio of 4:1:0.05) for 48 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 sulfate 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 preset at a desired temperature, 800° C.-1,100° C. for 30-90 seconds to obtain gr...

example 2

Oxidation and Exfoliation of Natural Graphite

[0149]Graphite oxide was prepared by oxidation of graphite flakes with sulfuric acid, sodium nitrate, and potassium permanganate at a ratio of 4:1:0.05 at 30° C. for 48 hours, according to the method of Hummers [U.S. Pat. No. 2,798,878, Jul. 9, 1957]. Upon completion of the reaction, the mixture was poured into deionized water and filtered. The sample was then washed with 5% HCl solution to remove most of the sulfate ions and residual salt and then repeatedly rinsed with deionized water until the pH of the filtrate was approximately 4. The intent was to remove all sulfuric and nitric acid residue out of graphite interstices. The slurry was dried and stored in a vacuum oven at 60° C. for 24 hours.

[0150]The dried, intercalated (oxidized) compound was exfoliated by placing the sample in a quartz tube that was inserted into a horizontal tube furnace preset at 1,050° C. to obtain highly exfoliated graphite. The exfoliated graphite was disperse...

example 3

Preparation of Pristine Graphene Sheets

[0152]Pristine graphene sheets were produced by using the direct ultrasonication or liquid-phase exfoliation process. In a typical procedure, five grams of graphite flakes, ground to approximately 20 μm in sizes, were dispersed in 1,000 mL of deionized water (containing 0.1% by weight of a dispersing agent, Zonyl® FSO from DuPont) to obtain a suspension. An ultrasonic energy level of 85 W (Branson 5450 Ultrasonicator) was used for exfoliation, separation, and size reduction of graphene sheets for a period of 15 minutes to 2 hours. The resulting graphene sheets were pristine graphene that had never been oxidized and were oxygen-free and relatively defect-free. There are substantially no other non-carbon elements. These graphene sheets were used as a conducting material in the core or as a shell carbonaceous / graphitic material.

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Abstract

Provided is a method of producing multiple anode particulates, comprising: a) dispersing an electrically conducting material, primary particles of an anode active material, an optional electron-conducting material, and a sacrificial material in a liquid medium to form a precursor mixture; b) forming the precursor mixture into droplets and drying the droplets; and c) removing the sacrificial material or thermally converting the sacrificial material into a carbon material to obtain multiple particulates, wherein a particulate comprises one or a plurality of anode active material particles having a volume Va, an electron-conducting material, and pores having a volume Vp which are encapsulated by a thin encapsulating layer having a thickness from 1 nm to 10 μm and a lithium ion conductivity from 10−8 S / cm to 5×10−2 S / cm and the volume ratio Vp / Va in the particulate is from 0.3 / 1.0 to 5.0 / 1.0.

Description

[0001]The present invention relates generally to the field of rechargeable lithium battery and, more particularly, to the anode active materials in the form of particulates secondary particles containing a core of anode active material primary particles and pores encapsulated by a thin shell (a thin encapsulating layer) containing a carbonaceous or graphitic material and a method of producing same.BACKGROUND OF THE INVENTION[0002]A unit cell or building block of a lithium-ion battery is typically composed of an anode current collector, an anode or negative electrode layer (containing an anode active material responsible for storing lithium therein, a conductive additive, and a resin binder), an electrolyte and porous separator, a cathode or positive electrode layer (containing a cathode active material responsible for storing lithium therein, a conductive additive, and a resin binder), and a separate cathode current collector. The electrolyte is in ionic contact with both the anode ...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): H01M4/36H01M10/0525H01M10/058H01M4/587
CPCH01M2004/027H01M4/483H01M10/058H01M10/0525H01M4/523H01M4/366H01M4/587H01M4/387H01M4/386H01M4/0447H01M4/38H01M4/382H01M4/405H01M4/62H01M4/622H01M4/623H01M4/624H01M4/625H01M4/626H01M10/049H01M10/446Y02E60/10Y02P70/50
Inventor JANG, BOR Z.
Owner GLOBAL GRAPHENE GRP INC
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