Solid Electrolyte Gradient for Li Metal Battery Stability

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Solution Overview

Problem

Lithium secondary batteries with metallic Li and sulfide-based solid electrolytes face challenges in achieving high capacity and stable charge/discharge cycling characteristics, particularly at low temperatures, due to electrochemical instability and limited heat resistance.

Innovation Solution

A battery structure with a solid electrolyte layer composed of Li, phosphorus, boron, sulfur, oxygen, and nitrogen, featuring a two- or three-layered configuration with controlled atomic fractions and functional gradients, enhancing electrochemical stability and ionic conductivity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If metallic Li is used for a negative electrode in batteries using an organic electrolytic solution, then discharge capacity per unit volume is improved, but charge/discharge cycling characteristics deteriorate due to needle crystal formation and short circuiting

Engineering Contradiction:
Improvedischarge capacity per unit volumeVSAvoidcharge/discharge cycling characteristics
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The invention changes the physical state parameter of the electrolyte from liquid (organic electrolytic solution) to solid (solid electrolyte layer), which fundamentally alters the interaction between Li metal and the electrolyte. This parameter change prevents needle crystal formation and maintains electrochemical stability during repeated charging and discharging cycles.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention uses a composite structure consisting of a solid electrolyte layer (made from Li compounds containing P, S, O, and Nb/Ta) in contact with the Li metal negative electrode. This composite material system provides both high capacity and stable cycling characteristics by combining the high capacity advantage of Li metal with the stability advantage of solid electrolytes.

Inventive Principle:
Principle #40Composite materials

2Quantity of substance

If batteries using an organic electrolytic solution are designed for high capacity, then discharge capacity is improved, but heat resistance deteriorates and cannot withstand reflow solder mounting process temperatures

Engineering Contradiction:
Improvedischarge capacityVSAvoidheat resistance
Core Design Contradiction:
Quantity of substanceVSTemperature

Solution Approach 1:

The invention changes the electrolyte from liquid organic solution to solid state material, which fundamentally improves the thermal stability and heat resistance of the battery system, enabling it to withstand reflow solder mounting process temperatures while maintaining high discharge capacity.

Inventive Principle:
Principle #35Parameter changes

3Temperature

If Li metal is used in batteries requiring improved heat resistance, then melting point concerns arise at about 180° C., but solid electrolyte provides sufficient heat resistance in reflow solder mounting process

Engineering Contradiction:
Improveheat resistance in reflow solder mounting processVSAvoidelectrochemical stability of Li
Core Design Contradiction:
TemperatureVSReliability

Solution Approach 1:

The solid electrolyte layer acts as an intermediary barrier between the Li metal negative electrode and the external environment. This intermediary layer protects the Li metal from direct exposure to high temperatures and reactive substances, maintaining electrochemical stability while enabling the battery to withstand reflow solder mounting process temperatures.

Inventive Principle:
Principle #24Intermediary (Mediator)

4Power

If sulfide-based solid electrolytes are used to improve ionic conductivity, then current density is improved, but electrochemical stability against negative electrode containing metallic Li deteriorates

Engineering Contradiction:
Improvecurrent densityVSAvoidelectrochemical stability
Core Design Contradiction:
PowerVSReliability

Solution Approach 1:

The invention uses a composite solid electrolyte material system containing Li compounds with P, S, O, and Nb/Ta elements. This composite material combines the high ionic conductivity advantage of sulfide-based electrolytes with the electrochemical stability provided by phosphate and oxide components, achieving both high current density and stable cycling characteristics.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention introduces local compositional variations within the solid electrolyte layer, with different regions having optimized compositions for specific functions. The solid electrolyte contains P and S for ionic conductivity, while O and Nb/Ta provide electrochemical stability, creating local quality differences that address multiple requirements simultaneously.

Inventive Principle:
Principle #3Local quality

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The battery structure achieves high current density and stable charge/discharge cycling characteristics at low temperatures, with improved lithium ionic conductivity and reduced degradation, ensuring increased capacity and efficiency.

Implementation Method 1

the solid electrolyte layer has a chemical composition... aLi·bX·cS·dY... improving lithium ionic conductivity

Methodology Applied
Scientific EffectIonic conduction: Conduction (electrical)

Implementation Method 2

a solid electrolyte layer is disposed between a positive electrode layer... and a negative electrode layer... the metallic Li may react with the organic electrolytic solution to form needle crystals

Methodology Applied
Scientific EffectPhysical barrier: Physical Containment

Data Source

PatentUS8021790B2Battery structure and lithium secondary battery using the same
Publication Date: 2011.09.20 SUMITOMO ELECTRIC INDUSTRIES LTD

AI summary

A battery structure includes a positive electrode layer, a solid electrolyte layer, and a negative electrode layer disposed in that order, wherein the solid electrolyte layer has a chemical composition, excluding incidental impurities, represented by the formula aLi·bX·cS·dY, where X is at least one element of phosphorus (P) and boron (B), Y is at least one element of oxygen (O) and nitrogen (N), the sum of a, b, c, and d is 1, a is 0.20 to 0.52, b is 0.10 to 0.20, c is 0.30 to 0.55, and d is 0 to 0.30. The solid electrolyte layer includes a portion A in contact with the negative electrode layer and a portion B in contact with the positive electrode layer, and d in the portion A is larger than d in the portion B. A lithium secondary battery includes the battery structure.