CN106443477A - Method of predicting the residual life of lithium battery - Google Patents
Method of predicting the residual life of lithium battery Download PDFInfo
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- CN106443477A CN106443477A CN201610934627.3A CN201610934627A CN106443477A CN 106443477 A CN106443477 A CN 106443477A CN 201610934627 A CN201610934627 A CN 201610934627A CN 106443477 A CN106443477 A CN 106443477A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method of predicting the residual life of a lithium battery. The method of predicting the residual life of a lithium battery includes the following steps: preparing one housing which is identical to a lithium battery before using, and a gas cylinder which is connected with the outside of the housing and is provided with a pressure gauge; filling inert gas to expand and deform the housing; establishing a function relational expression about the expansion degree and the pressure data displayed by the pressure gauge, wherein the pressure data displayed by the pressure gauge is equal to the value of the internal pressure of the lithium battery; according to an ideal gas state equation PV=nRT and the known parameters, calculating the amount n1 of substance of the gas in the lithium battery after using, n1 =p'v3'/RT'; calculating the amount n2 of substance of the consumed active substance required by generation of the gas; and calculating the amount n3 of substance of the total active substance before the electrochemical reaction to obtain the residual life (1-n2/n3*100%). The method of predicting the residual life of a lithium battery is simple and effective, and is specifically suitable for predicting the residual life of an irregular lithium primary battery (non-standard piece).
Description
Technical field
The present invention relates to a kind of Forecasting Methodology of lithium battery residual life, more particularly, to one kind is by setting up functional relation
Method to predict lithium primary battery residual life.
Background technology
Lithium primary battery (primary lithium battery), is a kind of high-energy chemistry galvanic cell, is commonly called as lithium battery.
With lithium metal as negative pole, solid salt or the salt being dissolved in organic solvent are electrolyte, metal oxide or other solids, liquid
Oxidant is positive electrode active material.
The main material of lithium battery is negative material typically with lithium metal or lithium alloy, because lithium metal is that one kind is vivaciously golden
Belong to, meet water and can discharge hydrogen by intense reaction, so this kind of lithium battery must adopt nonaqueous electrolyte, they are generally by organic molten
Agent and inorganic salts composition, there is not lasting chemical reaction as principle with lithium and battery other materials, conventional LiClO4、
LiAsF6、LiAlCl4、LiBF4, the inorganic salts such as LiBr, LiCl make the electrolyte of lithium battery, and organic solvent be usually then use PC,
In EC, DME, BL, THF, AN, MF two, three kind of mixing uses as organic solvent.The positive active material of lithium battery is commonly used
Have：Solid-state halide such as copper fluoride (CuF2), copper chloride (CuCl2), silver chlorate (AgCl), poly- fluorocarbons ((CF)4), solid-state sulphur
Compound such as copper sulfide (CuS), iron sulfide (FeS), ferrous disulfide (FeS2), solid-oxide such as manganese dioxide (MnO2), cupric oxide
(CuO), molybdenum trioxide (MoO3), vanadic anhydride (V2O5), solid-state oxysalt such as siliver chromate (Ag2CrO4), bismuthic acid lead
(Pb2Bi2O5), solid-state halogen such as iodine (I2), liquid oxygen compound such as sulfur dioxide (SO2), liquid oxyhalide such as thionyl chloride
(SOCl2).Therefore lithium primary battery has a lot of series, common are lithium-manganese dioxide, lithium-copper sulfide, lithium-fluorocarbons, lithium-
Sulfur dioxide and lithium-thionyl chloride etc..
This parameter of the residual capacity of conventional lithium primary battery is very important, and it can point out remaining of consumer batteries
The remaining life-span can also use how must change lithium battery long afterwards.Generally researcher is to calculate electricity by the application model of battery
The capacity that pond consumes, thus drawing battery remaining power, calculates residual life.
But the application model of equipment is usually relatively complex under actual conditions, it is difficult to accurately calculate the appearance of battery consumption
Amount.
Content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of lithium battery residual life
Forecasting Methodology, more particularly, to a kind of functional relation by setting up lithium battery dilation and internal pressure is once electric to predict lithium
The method of pond residual life.Especially effective especially for special-shaped lithium primary battery (non-standard), battery manufacture producer can be right
Each Special-shaped battery provides a reference curve, and consumer can carry out calculating the surplus of battery according to the reference curve providing
Covolume amount, thus draw the residual life of battery.
For reaching this purpose, the present invention employs the following technical solutions：
A kind of Forecasting Methodology of lithium battery residual life, the method comprising the steps of：
(1) shell of preparation one and the enclosure material using front lithium battery, cumulative volume, cavity volume, the thick all same of shell
Body, described housing fully seals in addition to liquid injection port；
(2) described liquid injection port is sealed with one end of seal, the other end of seal connects equipped with manometric
Gas cylinder, equipped with inert gas in described gas cylinder；
(3) open gas cylinder, in housing, be filled with inert gas, to full of housing；
(4) continue to be filled with inert gas in housing, housing expands deformation, the housing cumulative volume before expansion is v, swollen
Expansibility is the cumulative volume v after x and expansion*And the relation of v is：X=(v*- v)/v, record the described pressure gauge when dilation is for x and show
The pressure data p showing, is designated as (x, p)；
(5) dilation obtaining step (4) and pressure data are fitted, and obtain dilation x and the letter of pressure data p
Number relational expression；
(6) measurement is respectively v using the cumulative volume of lithium battery in front and back1' and v2', wherein, v2' be using temperature T ' under
Record, dilation is x '=(v2’-v1’)/v1The functional relation that ', by dilation x ' substitutes into step (5) is calculated use
Internal pressure p of lithium battery afterwards '；
Calculate cavity volume v of the lithium battery after using3', according to The Ideal-Gas Equation PV=nRT, it is calculated
The amount of the material of gas that the lithium battery interior after use produces is n1=p ' v3’/RT’；
(7) according in electro-chemical reaction equations, between the amount of the material of the gas of generation and the active material of consumption
Relation, calculates amount n of the material of active material participating in reaction2, the amount of the material of active material before note electrochemical reaction
For n3, then the residual life of lithium battery to be measured is (1-n2/n3) × 100%.
In the present invention, dilation x that step (5) obtains and the functional relation of pressure data p are temperature independent, any
At a temperature of (such as -40 DEG C～85 DEG C) be satisfied by this relational expression.
Preferably, described lithium battery is lithium thionyl chloride cell, lithium manganese dioxide cell, lithium fluorocarbon battery or lithium vanadic acid
Any one in silver battery.But it is not limited to the above-mentioned lithium primary battery enumerated, others produce gas through electrochemical reaction
The battery of body is also applied for the method for the present invention.
Preferably, the enclosure material of described lithium battery is any one in steel, stainless steel or titanium alloy.
Preferably, described inert gas be nitrogen, helium, neon, argon gas, in Krypton or xenon any one or at least
Two kinds of combination.
In the present invention, expand the cumulative volume v of front and rear housings1And v2Computational methods can adopt method of the prior art
Measure and calculate, it would however also be possible to employ following preferred version measures and calculates：
The cumulative volume v of described housing before expansion1Computational methods be：The length and width of housing before measurement expansion and height, respectively
It is designated as a1、b1And c1, then expand the cumulative volume v of procapsid1=a1b1c1；
The cumulative volume v of described housing after expansion2Computational methods be：The length and width of housing after measurement expansion and height, respectively
It is designated as a2、b2And c2, then expand the cumulative volume v of back casing2=a2b2c2.
Preferably, the method that matching adopts is any one in curve-fitting method or linear fit method, preferably
Curve-fitting method.
In the present invention, using the cumulative volume v of front lithium battery1' and use after lithium battery cumulative volume v2' calculating side
Method can be measured and be calculated using method of the prior art, it would however also be possible to employ following preferred version measures and counts
Calculate：
The described cumulative volume v using front lithium battery1' computational methods be：Measurement using the front length of li battery shell,
Wide and high, it is designated as a respectively1’、b1' and c1', then using the cumulative volume v of front lithium battery1'=a1’b1’c1’；
Lithium battery cumulative volume v after described use2' computational methods be：Measurement use after the length of the shell of lithium battery,
Wide and high, it is designated as a respectively2’、b2' and c2', then the lithium battery cumulative volume v after using2'=a2’b2’c2’.
Preferably, during step (4) record pressure data, at least three groups dilations and pressure data (x, p) are recorded, record
Group number is more, then the precision of matching is higher, is more beneficial for reacting the relation between dilation and pressure data exactly.
Preferably, cavity volume v of the lithium battery after described use3' calculate by the following method：After using
The cumulative volume v of lithium battery2' deduct the volume shared by intraware of lithium battery, obtain v3’.
Preferably, described use temperature T '=- 40 DEG C～85 DEG C, such as -40 DEG C, -30 DEG C, -20 DEG C, -15 DEG C, -10
DEG C, -5 DEG C, 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 65 DEG C, 75 DEG C or 85 DEG C
Deng.
By means of the invention it is also possible to obtain the dilation of battery and the relation of residual life, take multiple measurements, obtain
To the dilation of at least three Battery packs and residual life data, carry out linear or curve matching, can get battery dilation and
The relation curve of residual life.
If providing the specific discharge capacity data of battery and the quality of the active material of battery, understand the total capacity of battery,
Thus by the residual life of battery, the residual capacity of battery can be calculated, that is,：Residual capacity=(specific discharge capacity ×
The quality of active material) × residual life.
Compared with the prior art, the present invention has the advantages that：
(1) the method for the invention is held with the enclosure material using front lithium battery, cumulative volume, inner chamber by preparing one
Connect one outside the housing of the thick all same of long-pending and shell, with housing and carry manometric gas cylinder, being filled with inert gas makes housing generation swollen
Bulging becomes, and sets up dilation and the functional relation of pressure data that pressure gauge shows, and this relational expression can truly reflect very much
The relation of the internal pressure of the dilation of lithium battery and lithium battery, thus according to The Ideal-Gas Equation PV=nRT and
Know parameter (lithium battery interior pressure p ', volume v under lithium battery operating temperature3', lithium battery work temperature ') calculate use
Amount n of the material of the gas of lithium battery interior afterwards1=p ' v3'/RT ', calculates further and produces what these gases needs consumed
Amount n of the material of active material2, because the amount of the material of total active material before electrochemical reaction is n3, can obtain residual life is
(1-n2/n3) × 100%, and then the relation curve of cell expansion degree and residual life can be provided.
(2) method of the calculating battery remaining power that the present invention provides is simply effective, easy to operate, can be at the beginning of battery design
Phase is just previously obtained the relation reference curve of battery remaining power and cell expansion degree, and consumer is according to this reference curve oneself just
Energy simple computation goes out the residual life of battery.Solve the problems, such as that lithium primary battery residual capacity and residual Life Calculation are difficult.
Brief description
Fig. 1 is the fitted figure of pressure data that the embodiment of the present invention 1 obtains and dilation.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1
The existing one piece used lithium thionyl chloride cell having certain dilation (is designated as mesuring battary, it uses temperature
For 25 DEG C), (known specific discharge capacity is 3.86Ah/g, and the quality of active material is to need to survey its residual life and residual capacity
1.96g).
The method of prediction residual life and residual capacity is as follows：
(1) take one piece of battery that same batch produces with mesuring battary, this block battery with the use of front mesuring battary is one
Sample, it is designated as battery A.
One enclosure material with battery A of preparation, the housing of cumulative volume, cavity volume and the thick all same of shell, described housing
On fully seal in addition to liquid injection port；
(2) liquid injection port is sealed with one end of seal, the other end of seal connects equipped with manometric gas cylinder,
Equipped with inert gas in gas cylinder；
(3) open gas cylinder, in housing, be filled with inert gas, to full of housing；
(4) continue to be filled with inert gas in housing, housing expands deformation, the housing cumulative volume before expansion is v, swollen
Cumulative volume v after expansibility x and expansion*And the relation of v is：Dilation x=(v*- v)/v, record described pressure when dilation is for x
The pressure data p that table shows, is designated as (x, p), the results are shown in Table 1：
Table 1
| Pressure data/MPa that pressure gauge shows | Box hat dilation/% |
| 0.4 | 14.72 |
| 0.6 | 18.58 |
| 0.8 | 20.98 |
Because battery A all seals in addition to liquid injection port, and liquid injection port pass through seal with full of inert gas and dress
Barometric gas cylinder is had to connect, the pressure data that pressure gauge shows just truly reflects the pressure in battery A.
(5) dilation obtaining step (4) and pressure data are fitted, and obtain dilation x and the letter of pressure data p
Number relational expression, y=0.0906ln (x)+0.2308, wherein degree of fitting R2=0.9987 (fitting result is shown in Fig. 1).
(6) measure the cumulative volume v1 ' of the battery A and cumulative volume v of mesuring battary2', wherein, v2' be using temperature T '
Record under the conditions of=25 DEG C, being calculated dilation is x '=(v2’-v1’)/v1'=18%, dilation 18% is substituted into step
Suddenly functional relation y=0.0906ln (x)+0.2308 that (5) obtain, the internal pressure of the mesuring battary obtaining be y=p '=
0.574MPa；
Calculate cavity volume v of the lithium battery after using3'=172.74cm3.
According to The Ideal-Gas Equation PV=nRT, in formula, R is ideal gas constant, is 8.314J mol-1K-1, calculate
Amount n of the material of sulfur dioxide gas producing inside the lithium thionyl chloride cell after being used1=p ' v3'/RT '=
0.04mol.
Reaction equation according to lithium thionyl chloride cell：
4Li(s)+2SOCl2(l)→4LiCl(s)+SO2(g)+S(s)
Because lithium thionyl chloride cell design is limit anode (lithium piece) design, therefore when the lithium piece weight of the battery of design is
During 1.96g (1.96g*3.86Ah/g=7.5Ah), the amount of the material of the sulfur dioxide gas generating in theory is 0.0705mol,
It is 0.04mol/0.0705mol=56.73% that the reaction of therefore this lithium battery (mesuring battary) carries out degree, and that is, this battery is surplus
The remaining life-span is (100%-56.73%)=43.26% of initial lifetime.
The residual capacity of this lithium battery (mesuring battary) is 7.5Ah × 43.26%=3.2445Ah.
Further, measure the corresponding residual life of difference under multiple dilations, can be by multigroup dilation and residue
The data matching in life-span obtains the curve of dilation and residual life.
Further, measure the corresponding residual capacity of difference under multiple dilations, can be by multigroup dilation and residue
The data matching of capacity obtains the curve of dilation and residual capacity.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, that is, do not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, the equivalence replacement to each raw material of product of the present invention and auxiliary element
Interpolation, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. a kind of Forecasting Methodology of lithium battery residual life is it is characterised in that the method comprising the steps of：
(1) one housing with the enclosure material using front lithium battery, cumulative volume, cavity volume and shell thickness all same of preparation,
Fully seal in addition to liquid injection port on described housing；
(2) described liquid injection port is sealed with one end of seal, the other end of described seal connects equipped with manometric
Gas cylinder, equipped with inert gas in described gas cylinder；
(3) open gas cylinder, in described housing, be filled with inert gas, to full of housing；
(4) continue to be filled with inert gas in described housing, housing expands deformation, the housing cumulative volume before expansion is v, swollen
Cumulative volume v after expansibility x and expansion*And the relation of v is：Dilation x=(v*- v)/v, record described pressure when dilation is for x
The pressure data p that table shows, is designated as (x, p)；
(5) dilation obtaining step (4) and pressure data are fitted, and obtain dilation x and the function of pressure data p closes
It is formula；
(6) measurement is respectively v using the cumulative volume of lithium battery in front and back1' and v2', wherein, v2Record under ' be using temperature T '
, dilation is x '=(v2’-v1’)/v1The functional relation that ', by dilation x ' substitutes into step (5) is calculated after use
Internal pressure p of lithium battery '；
Calculate cavity volume v of the lithium battery after using3', according to The Ideal-Gas Equation PV=nRT, after being calculated use
Lithium battery interior produce the material of gas amount n1=p ' v3’/RT’；
(7) according in electro-chemical reaction equations, relation between the amount of the material of the gas of generation and the active material of consumption,
Calculate amount n of the material of active material participating in reaction2, before note electrochemical reaction, the amount of total material of active material is n3,
The residual life of the lithium battery after then using is (1-n2/n3) × 100%.
2. method according to claim 1 is it is characterised in that described lithium battery is lithium thionyl chloride cell, lithium titanium dioxide
Any one in manganese cell, lithium fluorocarbon battery or lithium vanadic acid silver battery.
3. method according to claim 1 and 2 it is characterised in that described lithium battery enclosure material be steel, stainless steel or
Any one in titanium alloy.
4. the method according to any one of claim 1-3 is it is characterised in that described inert gas is nitrogen, helium, neon
In gas, argon gas, Krypton or xenon any one or at least two combination.
5. the method according to any one of claim 1-4 it is characterised in that expand before described housing cumulative volume v1Meter
Calculation method is：The length and width of housing before measurement expansion and height, are designated as a respectively1、b1And c1, then expand the cumulative volume v of procapsid1
=a1b1c1；
The cumulative volume v of described housing after expansion2Computational methods be：The length and width of housing after measurement expansion and height, are designated as respectively
a2、b2And c2, then expand the cumulative volume v of back casing2=a2b2c2.
6. the method according to any one of claim 1-5 is it is characterised in that the method that described matching adopts is curve matching
Any one in method or linear fit method, preferably curve-fitting method.
7. the method according to any one of claim 1-6 is it is characterised in that the described cumulative volume v using front lithium battery1’
Computational methods be：Measurement uses the front length and width of li battery shell and height, is designated as a respectively1’、b1' and c1', then using front
The cumulative volume v of lithium battery1'=a1’b1’c1’；
Lithium battery cumulative volume v after described use2' computational methods be：Measurement use after the length and width of the shell of lithium battery and
Height, is designated as a respectively2’、b2' and c2', then the lithium battery cumulative volume v after using2'=a2’b2’c2’.
8. the method according to any one of claim 1-7 is it is characterised in that when described step (4) records pressure data, remember
At least three groups dilations of record and pressure data.
9. the method according to any one of claim 1-8 is it is characterised in that the cavity volume of lithium battery after described use
v3' calculate by the following method：Cumulative volume v with the lithium battery after use2' deduct the body shared by intraware of lithium battery
Long-pending, obtain v3’.
10. the method according to any one of claim 1-9 is it is characterised in that described use temperature T '=- 40 DEG C～85
℃.
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| CN109975715A (en) * | 2019-03-08 | 2019-07-05 | 天津力神电池股份有限公司 | A kind of preparation method of lithium ion battery of electric automobile mould group remaining capacity |
| CN112965000A (en) * | 2021-02-01 | 2021-06-15 | 惠州亿纬锂能股份有限公司 | Method, device and system for predicting service life of battery |
| CN114114043A (en) * | 2021-10-29 | 2022-03-01 | 合肥国轩高科动力能源有限公司 | Swelling detection method in lithium battery circulation process |
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| CN114114043A (en) * | 2021-10-29 | 2022-03-01 | 合肥国轩高科动力能源有限公司 | Swelling detection method in lithium battery circulation process |
| CN114114043B (en) * | 2021-10-29 | 2023-10-10 | 合肥国轩高科动力能源有限公司 | Expansion detection method in lithium battery cycle process |
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|---|---|
| CN106443477B (en) | 2019-06-25 |
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