Lithium-Containing Silicon Negative Electrode Active Material

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Solution Overview

Problem

Lithium ion secondary batteries using silicon as a negative electrode material face challenges in achieving high battery capacity and cycle characteristics due to particle expansion, cracking, and electrolyte decomposition, leading to poor first time charge/discharge efficiency and cycle retention.

Innovation Solution

A production method for a negative electrode active material involving lithium-containing silicon compounds, where particles are treated with a solution containing lithium and ether-based solvents, followed by heating to stabilize the lithium insertion and form a carbon coating, optimizing the crystallite size and lithium content for improved efficiency and stability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If silicon is used as the negative electrode active material to improve battery capacity, then the theoretical capacity increases significantly, but particles expand and contract during charge/discharge causing cracks to occur

Engineering Contradiction:
Improvebattery capacityVSAvoidparticle integrity
Core Design Contradiction:
Quantity of substanceVSStrength

Solution Approach 1:

The patent applies the nesting principle by forming a core-shell structure where silicon particles are embedded within a carbon-containing layer. The silicon core provides high capacity while the surrounding carbon shell maintains structural integrity during expansion and contraction, preventing particle cracking and improving cycle characteristics.

Inventive Principle:
Principle #7Nested doll (Nesting)

Solution Approach 2:

The patent uses composite materials by combining silicon with carbon-containing materials to create a negative electrode active material. This composite structure allows the silicon to provide high theoretical capacity while the carbon component provides mechanical strength and structural stability, resolving the contradiction between capacity and particle integrity.

Inventive Principle:
Principle #40Composite materials

2Quantity of substance

If the superficial layer of particles is cracked due to expansion/contraction, then a new surface is generated increasing reaction area, but electrolytic solution is consumed through decomposition reactions

Engineering Contradiction:
Improvereaction areaVSAvoidelectrolytic solution consumption
Core Design Contradiction:
Quantity of substanceVSLoss of substance

Solution Approach 1:

The patent applies preliminary action by pre-forming a carbon-containing coating layer on the silicon particle surface before electrochemical cycling begins. This pre-formed protective layer prevents direct contact between the electrolytic solution and the silicon surface, eliminating decomposition reactions and electrolyte consumption while still allowing lithium ion transport.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The carbon-containing layer serves as an intermediary between the silicon particles and the electrolytic solution. It mediates the interaction by providing a stable interface that allows lithium ion diffusion while preventing harmful decomposition reactions, thus maintaining reaction area without electrolyte consumption.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Reliability

If a carbon material coating is provided on silicon oxide particles to improve safety and capacity, then battery performance improves, but the manufacturing process becomes more complex

Engineering Contradiction:
Improvebattery safety and capacityVSAvoidmanufacturing process complexity
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent merges the carbon coating formation with the electrode manufacturing process itself. By incorporating carbon-containing materials into the slurry mixture and forming the coating during the standard electrode fabrication process (coating, drying, and heating), the patent achieves improved battery performance without adding separate complex manufacturing steps.

Inventive Principle:
Principle #5Merging (Combining)

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 method enhances battery capacity, first time charge/discharge efficiency, and cycle characteristics by stabilizing the lithium insertion and reducing particle expansion, resulting in improved battery performance and stability.

Implementation Method 1

particles of silicon compound are brought into contact with a solution A to obtain particles of lithium-containing silicon compound

Methodology Applied
Scientific EffectAbsorption: Absorption (physical)

Implementation Method 2

the particles of silicon compound into which the lithium was inserted are brought into contact with a solution B or are heated

Methodology Applied
Scientific EffectHeating: Heating

Implementation Method 3

among Li inserted in the Li insertion by soaking, a component that reacts with water used when forming a negative electrode slurry is changed to a substance thermodynamically more stable by a thermal process

Methodology Applied
Scientific EffectThermal stabilization: Heat Treatment

Implementation Method 4

a carbon coating film is formed on the particles of silicon compound

Methodology Applied
Scientific EffectCarbonization: Pyrolysis

Data Source

PatentEP3444877B1Method for producing negative electrode active material for nonaqueous electrolyte secondary batteries and method for producing negative electrode for nonaqueous electrolyte secondary batteries
Publication Date: 2021.11.10 SHIN ETSU CHEMICAL CO LTD
  • EP3444877B1 patent drawingFigure 1~2
  • EP3444877B1 patent drawingFigure 3~4
  • EP3444877B1 patent drawing

AI summary

The present invention provides a production method of a negative electrode active material for non-aqueous electrolyte secondary batteries containing particles of lithium-containing silicon compound including: preparing particles of silicon compound containing a silicon compound (SiOx: 0.5≤x≤1.6); obtaining particles of lithium-containing silicon compound by making the particle of silicon compound contact with a solution A that contains lithium and has an ether-based solvent as a solvent; and heating the particles of the lithium-containing silicon compound. Thus, a production method of a negative electrode active material for non-aqueous electrolyte secondary batteries capable of increasing battery capacity of the negative electrode active material and capable of improving the first time efficiency and cycle characteristics is provided.