Cellulose Separator Phosphoric Esterification Thermal Shrinkage

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Solution Overview

Problem

Polyolefin-based fine-porous separators used in lithium secondary batteries are prone to thermal shrinkage at high temperatures, leading to potential short-circuits between electrodes, and existing safety measures are insufficient for high-energy density batteries.

Innovation Solution

A separator made from a cellulose derivative with a phosphoric acid residue, produced through phosphate-esterification or phosphite-esterification of cellulose, which exhibits reduced thermal shrinkage and enhanced safety by suppressing temperature increases during overcharge or impact.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If a polyolefin-based fine-porous separator is used, then the separator provides good ion conductivity and electrochemical stability, but it shrinks at high temperatures causing thermal short-circuit

Engineering Contradiction:
Improveion conductivity and electrochemical stabilityVSAvoidthermal shrinkage resistance
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The patent uses a composite structure consisting of a heat-resistant base layer (cellulose acetate or polyimide) combined with a porous coating layer containing lithium hydroxide. This composite structure provides both the thermal stability of the base layer and the ion conductivity of the porous coating, while the lithium hydroxide coating acts as a thermal shutdown mechanism to prevent short-circuits at high temperatures.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent changes the material composition parameters by replacing conventional polyolefin materials with heat-resistant materials having specific glass transition temperatures and thermal decomposition points. The coating layer porosity and lithium hydroxide content are optimized to achieve the desired balance between ion conductivity and thermal safety.

Inventive Principle:
Principle #35Parameter changes

2Quantity of substance

If the battery energy density is increased, then the battery capacity is improved, but abnormal heat generation occurs during overcharge

Engineering Contradiction:
Improvebattery capacityVSAvoidabnormal heat generation
Core Design Contradiction:
Quantity of substanceVSObject-generated harmful factors

Solution Approach 1:

The patent converts the potential harmful effect of high temperature into a beneficial safety feature by incorporating lithium hydroxide in the porous coating layer. When abnormal heat generation occurs during overcharge, the lithium hydroxide decomposes endothermically to absorb excess heat and simultaneously forms a shutdown layer that stops ion transport, thereby preventing thermal runaway while allowing high energy density operation.

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

3Stability of the object's composition

If a separator with high heat resistance is used, then thermal shrinkage is prevented, but the separator may not provide sufficient safety against oxidation/reduction reactions

Engineering Contradiction:
Improveheat resistanceVSAvoidprotection against oxidation/reduction
Core Design Contradiction:
Stability of the object's compositionVSReliability

Solution Approach 1:

The patent introduces a porous coating layer containing lithium hydroxide as an intermediary between the heat-resistant base layer and the electrolyte. This coating layer serves dual functions: it provides additional thermal stability and acts as a chemical barrier that prevents direct contact between the separator and reactive species in the electrolyte, thereby protecting against oxidation and reduction reactions while maintaining ion conductivity.

Inventive Principle:
Principle #24Intermediary (Mediator)

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 cellulose-based separator with phosphoric acid residues demonstrates improved thermal stability and safety, maintaining high discharge capacity while minimizing thermal shrinkage and internal short-circuits, thus ensuring safer and more reliable battery performance.

Implementation Method 1

Cellulose has an excellent property that prevents the occurrence of thermal shrinkage even if the temperature is set to be high such as near 180°C

Methodology Applied
Scientific EffectThermal stability:

Implementation Method 2

in order to suppress oxidation / reduction reaction of a hydroxyl group (-OH) of cellulose, a method in which the hydroxyl group of cellulose is esterified is proposed

Methodology Applied
Scientific EffectEsterification: Chemical Bonding

Implementation Method 3

a battery having small temperature increases due to overcharge or due to impact from the outside is desired

Methodology Applied
Scientific EffectHeat absorption: Heat Sink

Data Source

PatentEP2680342B1Separator for accumulators, and accumulator
Publication Date: 2019.03.27 NEC CORP
  • EP2680342B1 patent drawingFigure 1~2
  • EP2680342B1 patent drawingFigure 3
  • EP2680342B1 patent drawing

AI summary

The object of an exemplary embodiment of the invention is to provide a separator for an electric storage device which has small thermal shrinkage under high-temperature environment, and in which the increase of the battery temperature can be suppressed. An exemplary embodiment of the invention is a separator for an electric storage device, which comprises a cellulose derivative represented by a prescribed formula. The separator for an electric storage device can be obtained, for example, by treating a cellulose separator containing cellulose with a phosphate or a phosphite.