CN102195104B - Method for detecting batteries in precharging state - Google Patents
Method for detecting batteries in precharging state Download PDFInfo
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- CN102195104B CN102195104B CN201010131377.2A CN201010131377A CN102195104B CN 102195104 B CN102195104 B CN 102195104B CN 201010131377 A CN201010131377 A CN 201010131377A CN 102195104 B CN102195104 B CN 102195104B
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- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 56
- 239000003792 electrolyte Substances 0.000 claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 36
- 229910052744 lithium Inorganic materials 0.000 claims description 36
- 238000003825 pressing Methods 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000012797 qualification Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 42
- 238000012360 testing method Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
Abstract
The invention discloses a method for detecting batteries in a precharging state, comprising the following steps: A, injecting the same type of electrolytes with different masses into the same type of batteries, and then detecting the internal pressures Pi and Pj of each battery in the precharging state under the condition of stable internal pressure after the electrolyte is injected each time; B, calculating the surplus volume Vij inside the battery at the ith detection relatively to the jth detection; and C, after many detections are finished, obtaining the surplus volume at the ith detection relative to other detections, carrying out statistics on multiple surplus volumes, and then converting the statistic result into the standard volume of a gas generated in the precharging state under the condition of the stable internal pressure. The technical scheme provided by the invention is convenient to implement, good in maneuverability, high in accuracy and wide in application, and can be used to remarkably improve the qualification rate of the batteries and effectively decrease potential safety hazards.
Description
Technical field
The present invention relates to field of batteries, relate in particular to a kind of pre-charge state detection method of battery.
Background technology
Lithium ion battery is in charge and discharge process, electrolyte generation electrochemical reaction and can produce a large amount of gas at inside battery while forming SEI (solid electrolyte interface film), these gases can and be used and all bring certain potential safety hazard the manufacture of lithium battery.
For example, in the use procedure of cylinder type lithium battery; if the gas that inside battery produces is at short notice more; may cause the rotating sheet upset in CID (relief valve) protective device; or gases at high pressure break through the relatively weak relief valve of mechanical performance in hush panel, even cause whole battery explosion.
Lithium battery, in manufacture process, injects the electrolyte into after lithium battery, need to lead to too little current lithium battery is carried out to precharge, for detection of with identification battery performance, thereby avoid causing danger.
While injecting the electrolyte into the laggard line precharge of lithium battery, if fail to control exactly the situation such as pressure, volume of gas that inside battery produces, still face certain potential safety hazard and maybe may cause other adverse consequences.For example, for cylinder type lithium battery, if inside battery air pressure is excessive under pre-charge state, just there will be the accident of the rotating sheet upset in CID protective device, reduce the qualification rate of product; For quadrate lithium battery, although can adopt the production technology of fluid injection-precharge-fluid infusion-sealing to reduce the excessive impact that battery structure is brought of inside battery air pressure under pre-charge state, yet, there is sometimes the phenomenon that electrolyte overflows, not only pollute workshop condition, also may corrode production equipment.
Generally, lithium battery just, the selection of negative electrode material, different types of additive of introducing in electrolyte etc. is all the key factor that affects the quantity of inside battery generation gas in pre-charge process, therefore, need to be to difformity and volume, select the volume of lithium battery gas that inside battery produces under pre-charge state of different electrolytes, pressure and variable condition etc. thereof detect, by testing result, just adjusting lithium battery, negative electrode material, and the additive types in electrolyte etc., thereby guaranteeing on the basis of lithium battery performance, effectively control the gas that inside battery produces, reduce potential safety hazard.
Yet, in current actual production, only can utilize certain checkout equipment under pre-charge state, to detect the air pressure of lithium battery interior, because metal shell forms constraint to the expansion of lithium battery interior gas, the volume of shell changes hardly, therefore be difficult to the volume of the gas that under direct-detection pre-charge state, lithium battery interior produces, more cannot under certain state, obtain volume and the pressure of gas that lithium battery interior produces simultaneously.
Summary of the invention
The main technical problem to be solved in the present invention is, provides a kind of and is convenient to implement and the pre-charge state detection method of the battery that accuracy is high.
For solving the problems of the technologies described above, the invention provides a kind of pre-charge state detection method of battery, comprise the following steps:
A: the electrolyte of the same race of different quality is injected respectively to battery of the same race, detect each injection after electrolyte, described battery is issued to the internal pressure P of interior pressing when steady at pre-charge state
iand P
j;
B: calculate and detect for the i time with respect to the j time detection, the residual volume V of described inside battery
ij:
Wherein: m
iwhile being the i time detection, inject the quality of the electrolyte of battery; m
jwhile being the j time detection, inject the quality of the electrolyte of battery; ρ is the density of electrolyte, i ≠ j;
C: after repeated detection, obtain the residual volume detecting with respect to other detection for the i time, described a plurality of residual volumes are carried out after statistical disposition, statistics is changed into described battery and at pre-charge state, be issued to the normal volume of the gas that interior pressing produces when steady;
Or the residual volume by the i time detection with respect to other detection changes into respectively after normal volume, and described a plurality of conversion results are carried out to statistical disposition.Obtain described battery and be issued to the normal volume of the gas that interior pressing produces when steady at pre-charge state.
Preferably, described step C also comprises following sub-step:
C1: calculate the detection detecting with respect to every other time for the i time, the average residual volume of described inside battery
:
Wherein, n is for detecting number of times, n >=2;
C2: by described average residual volume
change into described battery and be issued to the normal volume V of the gas that interior pressing produces when steady at pre-charge state
0:
Wherein, P
iyiatWei unit.
Preferably, in described step B, m
iwhile being less than the detection of every other time, inject the quality of the electrolyte of described battery.
In described steps A, the order successively increasing progressively according to the quality of injecting electrolyte detects described battery; In described step B, i=1.
Described battery is cylinder type lithium battery or quadrate lithium battery.
In a kind of execution mode, the size of described pre-charge current is 0.2C; Be 1 hour described precharge time.
The invention has the beneficial effects as follows: detection method provided by the invention has overcome prior art cannot direct-detection battery inner problem that produces the volume of gas under the pre-charge state, not only be convenient to implement, operability is good, and accuracy is high, of many uses, can significantly improve the qualification rate in electrogenesis pond, effectively reduce potential safety hazard.
Accompanying drawing explanation
Fig. 1 is that the flexible-packed battery that the present invention is 583346 to model carries out the change in volume schematic diagram detecting for three times;
Fig. 2 is that the flexible-packed battery that the present invention is 654173 to model carries out the change in volume schematic diagram detecting for three times;
Fig. 3 is the internal pressure checkout gear schematic diagram of the lithium battery of an embodiment of the present invention;
Fig. 4 is the flow chart of the pre-charge state detection method of a kind of battery of the present invention;
Fig. 5 is in one embodiment of the present invention, and the lithium battery that is 18650-2.2Ah to model carries out the pressure change schematic diagram detecting the 1st time;
Fig. 6 is in one embodiment of the present invention, and the lithium battery that is 18650-2.2Ah to model carries out the pressure change schematic diagram detecting the 2nd time;
Fig. 7 is in one embodiment of the present invention, and the lithium battery that is 18650-2.2Ah to model carries out the pressure change schematic diagram detecting the 3rd time;
Fig. 8 is in one embodiment of the present invention, and the lithium battery that is 18650-2.2Ah to model carries out the pressure change schematic diagram of the 4th detection.
Embodiment
Below by embodiment, by reference to the accompanying drawings the present invention is described in further detail.
For the lithium battery with metal shell, the volume that is difficult to its inner gas producing under pre-charge state of direct-detection, and for flexible-packed battery, the gas that electrolyte can be carried out to electrochemical reaction and produce in pre-charge process is filled with the air bag of variable volume, is therefore easy to detect by the change in volume of air bag the change in volume of the gas of inside battery generation.
Embodiment mono-:
As shown in Figure 1, the flexible package lithium cell that the present invention is 583346 to model carries out three pre-charge states and detects, pre-charge current is all 0.2C, and be all 1h precharge time, and the quality that detects the electrolyte of the same race that injects lithium battery for three times is respectively 3.40g, 3.26g and 2.94g.By the change in volume data of instant recording air bag, obtained the time m-change in volume figure of the gas that under pre-charge state, inside battery produces, in visible three testing processes, the volume that reaches the interior pressing gas that inside battery produces when steady when battery is approximately all 2.5ml.
As shown in Figure 2, the flexible package lithium cell that the present invention is 654173 to model again carries out three pre-charge states and detects, and pre-charge current and time are the same, and the electrolyte quality of the same race that detects injection lithium battery for three times is respectively 6.60g, 6.31g and 5.95g.The time m-change in volume data of the gas being produced from inside battery under pre-charge state, in three testing processes, the volume that reaches the interior pressing gas that inside battery produces when steady when battery is approximately all 5ml.
In conjunction with Fig. 1 and Fig. 2, limited number of time test data and analysis result show: for the battery with definite shape, size and capacity, in other words for battery of the same race, the quality of injecting the electrolyte of the same race of battery affects very little on the volume of the gas of inside battery generation under pre-charge state, very little on the amount of substance impact of the gas producing, its deviation is almost negligible.
Based on this, in conjunction with clapeyron equation:
PV＝nRT (1)
Wherein, P represents the pressure of gas, and unit is Pa; V represents the volume of gas, and unit is m
3; N represents amount of substance, and unit is that mol, T represent absolute temperature, and unit is K, and R represents gas constant, and for all gas, R is a fixed value.
Known for battery of the same race, even if inject the quality difference of the electrolyte of this battery, yet under the testing environment of temperature constant, because the amount of substance of the gas of inside battery generation under pre-charge state is identical, pressure and the amassing of volume of the gas that inside battery produces are a steady state value, obtain formula:
P
iV
i＝P
jV
j (2)
I and j represent respectively different detection number of times; The quality of the electrolyte injecting while detecting for the i time is m
i; The quality of the electrolyte injecting while detecting for the j time is m
j; P
iwhile representing to detect for the i time, under pre-charge state, battery reaches the internal pressure of interior pressing when steady; P
jwhile representing to detect for the j time, under pre-charge state, battery reaches the internal pressure of interior pressing when steady; V
ithe residual volume of inside battery under pre-charge state while representing to detect for the i time; V
jthe residual volume of inside battery under pre-charge state while representing to detect for the j time.
In fact, during each detection, after mixing, the air that the gas that under pre-charge state, inside battery produces in electrochemical reaction leaves with inside battery is contained in same remaining space, the volume of inside battery air when the residual volume that this remaining space is corresponding just equals not produce gas, the volume of battery container deducts the volume of electrolyte and volume core after fluid injection.Yet in actual application, cannot directly measure the residual volume of inside battery.
By existing measuring technique, can obtain the pressure P of inside battery
iand P
j, in a kind of execution mode, can measure respectively and obtain P by the pressure detection means shown in Fig. 3
iand P
j, particularly, the pressure of first setting the initial position of fluid column 1 is 1 atmospheric pressure (being 1at), then perforate on battery, utilize the air-tightness of fixture 2 assurance batteries, the changing condition of instant recording fluid column 1 in pre-charge process, thereby the pressure of definite inside battery.The P that this metering system obtains
iand P
junit be at.
In pre-charge process, inside battery forms a closed cavity, and therefore the difference of the volume of the gas of twice detection inside battery generation can draw according to following formula:
Wherein, the density that ρ is electrolyte.
Bring formula (3) into formula (2), can access and detect for the i time with respect to the j time detection, the residual volume V of inside battery
ij:
Based on this, as shown in Figure 4, the pre-charge state detection method of the battery of a kind of embodiment provided by the invention comprises the following steps:
S401: the electrolyte of the same race of different quality is injected respectively to battery of the same race, and inside battery can leave certain air conventionally, now the pressure of inside battery is 1 atmospheric pressure.Battery is carried out to precharge, and utilize the device shown in Fig. 3 or other modes, detect and to inject battery after electrolyte and reach the internal pressure P of interior pressing when steady at every turn
iand P
j, detect number of times and determine as required.
S402: according to formula (4), calculate and detect for the i time with respect to the j time detection, the residual volume V of inside battery
ij.
Consider test error, also should manage to reduce error by certain statistical, after repeated detection, obtain the residual volume detecting with respect to other detection for the i time, a plurality of residual volumes are carried out after statistical disposition, statistics is changed into this battery and at pre-charge state, be issued to gas that interior pressing the produces when steady normal volume under an atmospheric pressure;
Or, the residual volume detecting with respect to other detection for the i time is changed into respectively after normal volume, the normal volume of a plurality of conversions is carried out to statistical disposition, thereby obtain this battery, at pre-charge state, be issued to the normal volume of the gas that interior pressing produces when steady.
S403: in a kind of easy preferred implementation, after repeated detection, get the mean value that detects the residual volume obtaining with respect to every other detection for the i time, calculate the detection detecting with respect to every other time for the i time, the average residual volume of described inside battery
:
Wherein, n is for detecting number of times, n >=2.
Step S404: for the ease of comparing and analyzing, by the average residual volume of the inside battery calculating above
through calculating, be converted into gas that inside battery the produces normal volume V under an atmospheric pressure
0.By:
Wherein, P
0for standard atmospheric pressure, value is 1at, due to P
iye YiatWei unit, obtains:
In theory, because the quality size of electrolyte is very little on the volume impact of the gas of inside battery generation, so in detecting for n time, the detection of optional one-time detection with respect to every other time, the normal volume V finally obtaining
0should be steady state value, yet limited number of time result of the test shows, along with injecting the increase of the quality of electrolyte, inside battery is for holding corresponding the reducing in space of gas.Test error progressively increases, and therefore, in practice, the one-time detection that is preferably based on the quality minimum of injecting electrolyte is calculated, and gets m
ithe quality of the electrolyte injecting in battery while being less than the detection of every other time.
For example a kind of preferred embodiment in, the order that can successively increase progressively according to the quality of injecting the electrolyte of battery detects battery, chooses i=1 and calculates
, then pass through formula:
Obtain the normal volume of the gas of this kind of inside battery generation.
Embodiment bis-:
In the present embodiment, pressure and the volume of the cylinder type lithium battery that is 18650-2.2Ah to the model gas that inside battery produces under pre-charge state detect, and ρ is 1.235gcm
3.
First, by the pressure detection means shown in Fig. 3, divide and detect for 4 times after the electrolyte of the same race that injects different qualities, the internal pressure changing condition of battery of the same race under pre-charge state, use the electric current of 0.2C to charge respectively after 1h to each lithium battery, obtain the time m-pressure change curve chart of lithium battery interior under pre-charge state that each detection shown in Fig. 5 to Fig. 8 obtain.
According to curve chart, obtain following testing result:
| Number of times | 1 | 2 | 3 | 4 |
| Electrolyte quality (g) | 4.69 | 5.53 | 6.03 | 6.58 |
| Pressure when inner pressure of battery is stablized (at) | 2.46 | 3.235 | 3.944 | 5.44 |
The quality that detects the electrolyte adding in battery due to the 1st time is minimum, and in order to reduce error, present embodiment detects data based on the 1st time and calculates, and by formula (4), is obtained:
V
12＝2.84ml；V
13＝2.79ml；V
14＝2.88ml。
Obviously, between three numerical value, there is certain error, then by formula (5), calculated:
By formula (7), calculated again:
V
0＝4.15ml
Therefore draw, the cylinder type lithium battery that model is 18650-2.2Ah is under pre-charge state, and the volume of the gas that inside battery produces is 4.15ml.
By above account form, can obtain pressure and the volume of the gas that under pre-charge state, this inside battery produces simultaneously, thereby for judging and analyze the performance condition of battery, help technical staff to make corresponding adjustment to the kind of battery structure, electrolyte and additive etc.This detection mode has not only reduced potential safety hazard, and has effectively improved the qualification rate of product, avoids production environment to impact.
Detection method provided by the invention is not only convenient to implement, and operability is good, and accuracy is high, can be widely used in cylinder type lithium battery, quadrate lithium battery etc.
Above content is in conjunction with concrete execution mode further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (6)
1. a pre-charge state detection method for battery, is characterized in that, comprises the following steps:
A: the electrolyte of the same race of different quality is injected respectively to battery of the same race, detect each injection after electrolyte, described battery is issued to the internal pressure P of interior pressing when steady at pre-charge state
iand P
j;
B: calculate and detect for the i time with respect to the j time detection, the residual volume V of described inside battery
ij:
Wherein: m
iwhile being the i time detection, inject the quality of the electrolyte of battery; m
jwhile being the j time detection, inject the quality of the electrolyte of battery; ρ is the density of electrolyte, i ≠ j;
C: after repeated detection, obtain the residual volume detecting with respect to other detection for the i time, described a plurality of residual volumes are carried out after statistical disposition, statistics is changed into described battery and at pre-charge state, be issued to the normal volume of the gas that interior pressing produces when steady;
Or the residual volume by the i time detection with respect to other detection changes into respectively after normal volume, and described a plurality of conversion results are carried out to statistical disposition.Obtain described battery and be issued to the normal volume of the gas that interior pressing produces when steady at pre-charge state;
Described step C comprises following sub-step:
C1: calculate the detection detecting with respect to every other time for the i time, the average residual volume of described inside battery
Wherein, n is for detecting number of times, n >=2;
C2: by described average residual volume
change into described battery and be issued to the normal volume V of the gas that interior pressing produces when steady at pre-charge state
0:
Wherein, P
iyiatWei unit.
2. the method for claim 1, is characterized in that, in described step B, and m
iwhile being less than the detection of every other time, inject the quality of the electrolyte of described battery.
3. method as claimed in claim 2, is characterized in that, in described steps A, the order successively increasing progressively according to the quality of injecting electrolyte detects described battery; In described step B, i=1.
4. the method for claim 1, is characterized in that, described battery is cylinder type lithium battery or quadrate lithium battery.
5. the method for claim 1, is characterized in that, the size of described pre-charge current is 0.2C.
6. the method for claim 1, is characterized in that, be 1 hour described precharge time.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010131377.2A CN102195104B (en) | 2010-03-17 | 2010-03-17 | Method for detecting batteries in precharging state |
| HK12102034.0A HK1161656A1 (en) | 2010-03-17 | 2012-02-29 | An examining method of precharge state of the battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010131377.2A CN102195104B (en) | 2010-03-17 | 2010-03-17 | Method for detecting batteries in precharging state |
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| CN102195104A CN102195104A (en) | 2011-09-21 |
| CN102195104B true CN102195104B (en) | 2014-09-24 |
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| CN106154166A (en) * | 2015-04-17 | 2016-11-23 | 中国电力科学研究院 | The on-line measuring device of a kind of flexible packing lithium ion battery flatulence amount and detection method |
| CN107727529A (en) * | 2017-10-20 | 2018-02-23 | 合肥国轩高科动力能源有限公司 | Method for testing gas expansion rate of lithium ion battery in charging and discharging processes |
| CN110864758B (en) * | 2019-11-12 | 2020-12-18 | 桐乡乐维新材料有限公司 | Device and method for detecting gas production rate in graphene battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618142A (en) * | 2002-01-09 | 2005-05-18 | 史蒂文·E·斯鲁普 | System and method for removing an electrolyte from an energy storage and/or conversion device using a supercritical fluid |
| CN101673848A (en) * | 2008-09-11 | 2010-03-17 | 深圳市比克电池有限公司 | Method for manufacturing lithium-ion batteries |
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|---|---|---|---|---|
| US20030108785A1 (en) * | 2001-12-10 | 2003-06-12 | Wu L. W. | Meso-porous carbon and hybrid electrodes and method for producing the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618142A (en) * | 2002-01-09 | 2005-05-18 | 史蒂文·E·斯鲁普 | System and method for removing an electrolyte from an energy storage and/or conversion device using a supercritical fluid |
| CN101673848A (en) * | 2008-09-11 | 2010-03-17 | 深圳市比克电池有限公司 | Method for manufacturing lithium-ion batteries |
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| CN102195104A (en) | 2011-09-21 |
| HK1161656A1 (en) | 2012-07-27 |
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