CN105598044B - A kind of method of Effective selection self-discharge battery - Google Patents

A kind of method of Effective selection self-discharge battery Download PDF

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Publication number
CN105598044B
CN105598044B CN201510873015.3A CN201510873015A CN105598044B CN 105598044 B CN105598044 B CN 105598044B CN 201510873015 A CN201510873015 A CN 201510873015A CN 105598044 B CN105598044 B CN 105598044B
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battery
voltage
discharge
charging
self
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CN105598044A (en
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聂亮
厉蒋
左华通
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Hangzhou Botan New Energy Technology Co.,Ltd.
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Hangzhou Smooth Scientific And Technological Engineering Co Ltd Of Uncle
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B07SEPARATING SOLIDS FROM SOLIDS; SORTING
    • B07CPOSTAL SORTING; SORTING INDIVIDUAL ARTICLES, OR BULK MATERIAL FIT TO BE SORTED PIECE-MEAL, e.g. BY PICKING
    • B07C5/00Sorting according to a characteristic or feature of the articles or material being sorted, e.g. by control effected by devices which detect or measure such characteristic or feature; Sorting by manually actuated devices, e.g. switches
    • B07C5/34Sorting according to other particular properties
    • B07C5/344Sorting according to other particular properties according to electric or electromagnetic properties

Abstract

The present invention relates to a kind of method of Effective selection self-discharge battery, include the following steps:1. the low pressure state voltage knee of battery is determined using trickle charge method;It is electrically operated that 2. charge and discharge is carried out to battery, finally make the voltage of battery just at low pressure state voltage knee on, after cell voltage tends towards stability, measure the voltage OCV1 of each battery, and record;3. battery to be stored to a period of time under a design temperature, the voltage OCV2 of each battery is measured, and is recorded;4. calculating voltage drop value Δ the V=OCV1 OCV2, Δ V of each battery more than a setting value, the self-discharge battery filtered out is as needed.The method more science of the present invention, meet principle, self discharge lithium ion battery can be more accurately filtered out, while is decreased screened from battery irreversible capacity loss caused by discharge regime, so that it is guaranteed that chemical property excellent during the follow-up use of battery and security performance.

Description

A kind of method of Effective selection self-discharge battery
Technical field
The present invention relates to battery manufacturing field, more particularly to a kind of method of Effective selection self-discharge battery.
Background technology
Lithium ion battery self discharge refers to the battery phenomenon that voltage declines automatically during open circuit is stood, in various systems Electrode in, lithium ion battery self discharge phenomenon is inevitable.Lithium ion battery self discharge according to after capacitance loss whether It can recover to be divided into two kinds:Reversible capacity loses, and referring to can recover by charging process capacity again;Irreversible capacity damages Lose, represent that capacity cannot recover.
Influence self discharge degree because being known as many kinds, be roughly divided into:The preparation process of pole piece and battery, the property of electrolyte Matter and concentration, the storage temperature of battery and storage time etc..Self discharge speed can represent with lithium battery self-discharge rate, for The statement of lithium battery self-discharge rate is usually to be calculated with the capacitance loss of one month.Lithium ion battery is in certain charging state Under, the higher self discharge speed of temperature also can be faster.For example, lithium ion battery is under full electricity 100%SOC charging states, in room temperature bar Moon self-discharge rate under part is 3%, more than 55 DEG C at a high temperature of self-discharge rate can reach 10%, be at room temperature 3 times with On.In general, normal lithium ion battery self discharge is small, and caused capacitance loss can largely recover, in this case Self discharge belong to reversible capacity loss, as long as technological design is reasonable, battery consistency is preferable, it is believed that this self discharge category In normal phenomenon, battery normal use is not interfered with.But for irreversible capacitance loss, the electrochemistry of battery can be influenced Can, or even security risk can be caused, lead to not use, choose this battery so must be screened by self discharge.At present The self discharge screening technique that lithium ion battery manufacturer generally uses is full electricity is shelved under room temperature or high temperature by battery, is passed through After a while, judge that battery whether there is self discharge according to the pressure drop of battery.But this method is deposited in principle and technique In wretched insufficiency, or even can the final judgement that must be made mistake.
The content of the invention
Present invention mainly solves original lithium ion battery self discharge screening technique not science, exists in principle and technique tight Weight deficiency, cause non-self-discharge battery easily to be judged by accident, and really self-discharge battery but be difficult to the technical problem detected;There is provided A kind of method of Effective selection self-discharge battery, its method more science, can more accurately filter out self discharge lithium ion Battery, so that chemical property excellent during ensure that the follow-up use of battery and security performance.
The above-mentioned technical problem of the present invention is mainly what is be addressed by following technical proposals:A kind of effectively sieve of the invention Method selected from discharge battery, includes the following steps:
1. the low pressure state voltage knee of battery is determined using trickle charge method;
2. electrically operated to battery progress charge and discharge, last charged or electric discharge makes the voltage of battery just at low pressure state voltage On flex point, after cell voltage tends towards stability, the voltage OCV1 of each battery is measured, and record;
3. battery to be stored to a period of time under a design temperature, the voltage OCV2 of each battery is measured, and is recorded;
4. calculating the voltage drop value Δ V of each battery, Δ V=OCV1-OCV2, Δ V are as needed more than a setting value The self-discharge battery filtered out.
For lithium ion battery, in the case of full electricity, high pressure labile state is in inside battery system, in this case There are the factor that other can cause the decline of battery global voltage, as caused by self restructuring, battery process variations itself of SEI films Empty voltage height etc..And these cause the phenomenon of battery global voltage decline and are not belonging to irreversible self-discharge phenomenon, subsequently filling Battery system can gradually tend to balance in discharge process, and no longer there are the phenomenon that battery global voltage declines;In the case of half electricity, electricity Cell voltage is in flatter section, and the storage of short time accurately and efficiently can not screen self-discharge battery;Relatively low charged State, according to the discharge curve of battery it is known that curve is there are the gradient drastically to glide, i.e., there are a flex point, as long as There are self discharge, voltage declines, and just has larger voltage drop value, and so declining situation according to voltage just can be accurately and efficiently to certainly Discharge battery is screened.Meanwhile battery charge state is higher, irreversible loss is also bigger caused by the time is shelved, this is also Conventional method battery expires the important shortcoming that electricity shelves screening self discharge.
Since electric current is extremely faint in self-discharge processes, it is difficult to the low pressure state voltage knee of battery is found out in a short time, Therefore in the technical program, the low pressure state voltage knee of battery is determined using appropriate trickle charge method, is being determined After low pressure state voltage knee, by a kind of preferably mode make cell voltage just at the flex point on, treat cell voltage After tending towards stability, the initial voltage OCV1 of each battery is tested out, after battery stores a period of time at a certain temperature, then is surveyed The voltage OCV2 of each battery is tried out, finally calculates the voltage drop value Δ V of the battery in whole time, according to overall voltage drop value Situation carries out analysis judgement to self-discharge of battery, finally filters out underproof self-discharge battery.The method of the present invention more section Learn, can more accurately filter out self discharge lithium ion battery, while decrease screened from electric caused by discharge regime Pond irreversible capacity loss, so that chemical property excellent during ensure that the follow-up use of battery and security performance.
Preferably, 1. the step includes the following steps:
A. at ambient temperaturet, with charging/discharging apparatus to producing normal several full electric state batteries with 0.02~0.05C times For rate current discharge to empty electricity, C is battery total capacity, obtains the gross rated capacity value of battery;
B. at ambient temperaturet, it is small with the charging 0.5~1.5 of 0.02~0.05C multiplying powers electric current to each battery with charging/discharging apparatus When, stand 0.25~0.75 it is small when, survey cell voltage OCV, then with 0.02~0.05C multiplying powers electric current charging 0.5~1.5 it is small when, When standing 0.25~0.75 is small, cell voltage OCV is surveyed, so circulation 20~60 times, every time the total value of filled capacity divided by battery Nominal value is the charged state value SOC of battery after charging every time;
C. it is that X-axis makees OCV-SOC curve maps using OCV as Y-axis, SOC according to the data measured in step b;
D. the low pressure state voltage knee of battery is found out from OCV-SOC curve maps.
Electric current is extremely faint in self-discharge processes, it is difficult to the discharge curve under true self discharge is drawn out in a short time, The OCV-SOC curve maps of battery are drawn in the technical program using appropriate trickle charge method, easy to accurately find out The low pressure state voltage knee of battery.The charged state value SOC of battery, is also remaining capacity, represents battery and uses a period of time or long Phase lie idle after residual capacity and its fully charged state capacity ratio, commonly use percentage and represent, its value range For 0~1, represent that battery discharge is complete as SOC=0, represent that battery is completely filled with as SOC=1.
Preferably, 2. the step is:At ambient temperaturet, with the charging/discharging apparatus to each battery with 0.1~ 0.5C multiplying powers current discharge is to empty electricity, and C is battery total capacity, then at ambient temperaturet, with the charging/discharging apparatus to each electricity First with 0.1~0.2C multiplying power electric current constant-current charges, voltage reaches our setting value and then carries out constant-voltage charge in pond, until Current value is the cut-off of 0.02C multiplying powers, is finally made on 1. low pressure state voltage knee that the voltage of battery determines just at step, 1~3 it is small when after the voltage OCV1 of every battery is measured with battery measuring cell, and record.
Preferably, 3. the step is:Each battery is placed in a fixing tool, fixing tool extruding electricity The both ends in pond, battery is compressed, and battery and fixing tool are placed in the space of temperature-controllable, adjusts the temperature in the space Degree reaches temperature T2, and temperature T2 is higher than room temperature, battery and fixing tool is shelved under temperature T2 5~10 days;Then from fixation Battery is removed in frock, after temperature when battery temperature returns to measurement voltage OCV1, every electricity is measured with battery measuring cell The voltage OCV2 in pond, and record.In the technical program, T2 > T1, since temperature is higher, self-discharge of battery speed is faster, therefore OCV1 > OCV2.Fixing tool can be designed to clamp battery, can also be designed to that branched battery can be clamped at the same time, Using the fixing tool that can clamp branched battery at the same time, deal with it is more convenient, it is more efficient.
The beneficial effects of the invention are as follows:Method more science, meets principle, can more accurately filter out self discharge lithium Ion battery, while decrease screened from battery irreversible capacity loss caused by discharge regime, so that it is guaranteed that after battery Excellent chemical property and security performance during continuous use.The present invention is easy to operate, and device therefor is usual, can be repeatedly anti- It is multiple to use, overall lower cost.
Brief description of the drawings
Fig. 1 is a kind of dimensional structure diagram of the fixing tool for the clamping battery used in the present invention.
1. base in figure, 2. traverses, 3. pneumatic devices, 4. sliding slots, 5. sliding blocks.
Embodiment
Below with reference to the embodiments and with reference to the accompanying drawing the technical solutions of the present invention will be further described.
Embodiment:The method of a kind of Effective selection self-discharge battery of the present embodiment, to nickle cobalt lithium manganate (523)/artificial Graphite system flexible package 20Ah lithium ion batteries carry out self discharge screening, include the following steps:
1. the low pressure state voltage knee of battery is determined using trickle charge method:
A. at ambient temperaturet, it is (preceding to empty electricity with 100mA current discharges to producing normal branched battery with charging/discharging apparatus High current can be selected in phase electric discharge), obtain the gross rated capacity value of battery;
B. at ambient temperaturet, with charging/discharging apparatus to each battery with 100mA electric currents charging 1 it is small when, stand 0.5 it is small when, survey Cell voltage OCV, then with 100mA electric currents charging 1 it is small when, stand 0.5 it is small when, survey cell voltage OCV, so circulation 30 times, often The gross rated capacity value of secondary filled capacity divided by battery is the charged state value SOC of battery after charging every time;
C. it is that X-axis makees OCV-SOC curve maps using OCV as Y-axis, SOC according to the data measured in step b;
D. the low pressure state voltage knee of battery is found out from OCV-SOC curve maps.
2. at ambient temperaturet, T1 is less than 40 DEG C, (preceding to empty electricity with 4000mA current discharges to each battery with charging/discharging apparatus High current can be selected in phase electric discharge), then at ambient temperaturet, with charging/discharging apparatus to each battery with 4000mA electric current constant-current charges, Make on 1. low pressure state voltage knee that the voltage of battery determines just at step value nearby, using 3.5V to fill in the present embodiment Electric blanking voltage, then turns to the charging of constant pressure section, cut-off current 400mA, 2 it is small when after with battery measuring cell measure every battery Voltage OCV1, in the present embodiment, the final Initial Voltage Value OCV1 of battery is 3.495 ± 0.001V, and is recorded.
3. each battery is placed in a fixing tool, fixing tool used is as shown in Figure 1, including base in the present embodiment 1 and 12 pieces of traverses 2 parallel to each other on base 1.There is a sliding slot 4 on the top surface of base 1, sliding slot is the bottom of along The length direction extension of seat 1, the cross section semicircular in shape of sliding slot 4, sliding slot 4 is interior to be distributed equipped with 12 length directions along sliding slot Sliding block 5, sliding block 5 is semicylinder sliding block, and the semicylinder side of sliding block 5 matches downward and with semicircle sliding slot 4, sliding block 5 planar side upward, is vertically installed with one piece of traverse 2 in the planar side of each sliding block 5.The left side and the right side of base 1 Respectively there is a pneumatic device 3 realized by cylinder on side, and the leftmost side, the traverse 2 of the rightmost side are respectively and positioned at base on base 1 1 left side, the piston of cylinder on the right are connected.In use, soft-package battery is placed on to the sky between two adjacent traverses 2 one by one Between in, open pneumatic device 3, under a certain pressure traverse utilize slip of the semicylinder sliding block in sliding slot, most at last Each soft-package battery compresses.It is advisable in the present embodiment with that every cell thickness can be reduced 0.2mm.The whole series of battery will be clamped Frock is placed into the space of temperature-controllable, and the temperature in adjustment space reaches temperature T2, and in the present embodiment, T2 is 40 DEG C, is made Battery is shelved 7 days at a temperature of 40 DEG C;Then pneumatic device is opened, pressure is discharged, battery is removed from fixing tool, treats electricity When pond temperature returns to room degree T1, the voltage OCV2 of every battery is measured with battery measuring cell, and is recorded.
4. calculating voltage drop value Δ V, the Δ V=OCV1-OCV2 of each battery, battery is put certainly according to final voltage drop value Electric situation is judged that self-discharge battery voltage drop value is higher than normal battery, i.e. Δ V as needs to sieve more than a setting value The self-discharge battery selected.
It should be noted that method using the present invention, it is ensured that battery system to be screened, technique etc. it is consistent Property, because for the different battery of lithium battery system, manufacturing process, its final low pressure state voltage knee is different 's;At the same time in order to avoid end product is there are relatively large deviation, we will ensure in whole screening process temperature residing for battery, be made To be unified with equipment consistent.
Other electrochemical property tests are carried out to the battery by the present embodiment self discharge screening, the results showed that by this side The capacity of battery after method screening does not lose, other performances also do not change, the final certification reasonable validity of the method.
The present invention meets principle, and method more science, can more accurately filter out self discharge lithium ion battery, at the same time Decrease screened from battery irreversible capacity loss caused by discharge regime, so that it is guaranteed that excellent during the follow-up use of battery Different chemical property and security performance.The present invention is easy to operate, and device therefor is usual, can multiple Reusability, it is overall into This is less expensive, and cost performance is very high, requires higher and higher lithium electricity market to have in lithium ion battery electrochemistry and security performance Good application prospect.

Claims (1)

  1. A kind of 1. method of Effective selection self-discharge battery, it is characterised in that include the following steps:
    1. determining the low pressure state voltage knee of battery using trickle charge method, 1. step includes the following steps:
    A. at ambient temperaturet, with charging/discharging apparatus to producing normal several full electric state batteries with 0.02~0.05C multiplying powers electricity Stream is discharged to empty electricity, and C is battery total capacity, obtains the gross rated capacity value of battery;
    B. at ambient temperaturet, with charging/discharging apparatus to each battery with 0.02~0.05C multiplying powers electric current charging 0.5~1.5 it is small when, it is quiet Set to 0 .25~0.75 it is small when, survey cell voltage OCV, then with 0.02~0.05C multiplying powers electric current charging 0.5~1.5 it is small when, stand 0.25~0.75 it is small when, survey cell voltage OCV, so circulate 20~60 times, the total value constant volume of filled capacity divided by battery every time Value is the charged state value SOC of battery after charging every time;
    C. it is that X-axis makees OCV-SOC curve maps using OCV as Y-axis, SOC according to the data measured in step b;
    D. the low pressure state voltage knee of battery is found out from OCV-SOC curve maps;
    2. at ambient temperaturet, it is with 0.1~0.5C multiplying powers current discharge to empty electricity, C to each battery with the charging/discharging apparatus Battery total capacity, then at ambient temperaturet, with the charging/discharging apparatus to each battery first with 0.1~0.2C multiplying power electric current constant currents Charging, voltage reach we setting value and then carry out constant-voltage charge, until current value for 0.02C multiplying powers cut-off, finally make On 1. low pressure state voltage knee that the voltage of battery is determined just at step, 1~3 it is small when after it is every with the measurement of battery measuring cell The voltage OCV1 of branch battery, and record;
    3. each battery is placed in a fixing tool, the fixing tool extrudes the both ends of battery, battery is compressed, by battery And fixing tool is placed in the space of temperature-controllable, the temperature adjusted in the space reaches temperature T2, and temperature T2 is higher than room Temperature, makes battery and fixing tool be shelved under temperature T2 5~10 days;Then battery is removed from fixing tool, treats battery temperature After temperature when returning to measurement voltage OCV1, the voltage OCV2 of every battery is measured with battery measuring cell, and record;
    4. calculating voltage drop value the Δ V, Δ V=OCV1-OCV2, Δ V of each battery more than a setting value, as need to screen The self-discharge battery gone out.
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Patentee after: Hangzhou Botan New Energy Technology Co.,Ltd.

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Patentee before: HANGZHOU BOTAN TECHNOLOGY ENGINEERING Co.,Ltd.