CN107703167A - Active substance for positive electrode of lead-acid accumulator PAM analysis test methods - Google Patents
Active substance for positive electrode of lead-acid accumulator PAM analysis test methods Download PDFInfo
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- CN107703167A CN107703167A CN201710880712.0A CN201710880712A CN107703167A CN 107703167 A CN107703167 A CN 107703167A CN 201710880712 A CN201710880712 A CN 201710880712A CN 107703167 A CN107703167 A CN 107703167A
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Abstract
The present invention relates to a kind of active substance for positive electrode of lead-acid accumulator PAM analysis test methods, pass through the positive active material PAM Stratified Samplings to different charging states, analyzed with X-ray powder diffraction (XRD), and data processing is carried out using Rietveld Refinement instruments, draw the PbO of each sample2Weight/mass percentage composition, adopt gauss of distribution function to the PbO under different charging states, different layers2Content distribution curve be fitted, by the rate of change of active material reaction depth, come characterization board plate active material optimal charging state (depth of discharge) or not plates of similar polarity charging performance it is good and bad.The analysis method of the present invention, the cycle life size of battery and the quality of design are assessed by reaction depth, by the rate of change of reaction depth, determine the suitable depth of discharge of all kinds of design batteries.
Description
Technical field
The present invention relates to industrial lead-acid accumulator field, more particularly to a kind of active substance for positive electrode of lead-acid accumulator PAM
Analysis test method.
Background technology
Polar plate of lead acid storage battery active material does not have systematic analyzing evaluation method at present, can only be by observing outward appearance shape
PbO in shape, color, or analysis positive plate2Percentage, it is impossible to active material of the quantitative analysis pole plate under different charging states
Reaction depth size, the projected life of battery can only determine that the R&D cycle is oversize by the cyclic lifetime test results, it is impossible to
Pre-Evaluation is carried out to plate active material performance, research and development and the design of guide product improve.Therefore, a kind of lead-acid accumulator is invented
Positive active material PAM method for analyzing performance, is analyzed design and life-span Pre-Evaluation, to further optimization product knot
Structure and performance design, shorten the R&D cycle, reduce design work error, design long-life circular form battery is very necessary.
The content of the invention
The purpose of the present invention is the defects of overcoming prior art to exist, there is provided a kind of active matter for solving anode pole plate
The analysis method problem of matter, by the analysis and evaluation to pole plate performance, finds out optimal design, improves the cycle life of product, protects
Demonstrate,prove the active substance for positive electrode of lead-acid accumulator PAM analysis test methods of product reliability and best use effect.
Realizing the technical scheme of the object of the invention is:A kind of active substance for positive electrode of lead-acid accumulator PAM analysis test methods,
Comprise the following steps:
1) to the positive active material PAM Stratified Samplings of different charging states,
2) (XRD) is analyzed with X-ray powder diffraction,
3) data processing is carried out using Rietveld Refinement instruments,
4) PbSO of each sample is drawn4And PbO2Weight/mass percentage composition,
5) gauss of distribution function is adopted to the PbO under different charging states, different layers2Content distribution curve be fitted,
6) by the rate of change of active material reaction depth, to represent the depth of discharge of anode plate active material or not
The charging performance of plates of similar polarity is good and bad.
Step 1) described in above-mentioned technical proposal is specially:The anode plate of lead-acid accumulator is pressed to the electric discharge of different weight percentage
Electricity is discharged, and makes the anode plate of N kind difference charging states respectively, every kind of each 1, every pole plate is square along thickness d (mm)
To being uniformly divided into 5 layers, thickness sample point coordinates are 0.1d, 0.3d, 0.5d, 0.7d, 0.9d, are 0.2d (mm) per thickness degree,
The sampling of every layer of middle part, the sample position in length L directions is in 0.25L~0.75L, and the sample position in width B directions is in 0.25B
~0.75B, every layer is pressed upper, middle and lower, or left, center, right, samples at 3 points, and using after 3 sample mixeds as standard specimen, by lotus
When the number of plies is numbered electric state percentage respectively.
Step 5) described in above-mentioned technical proposal is specially:Gauss of distribution function is adopted to PbO2Content distribution curve intended
Close, take
σ=2.25-w/2 (mm)
Wherein, A is the integral area for the Gaussian function curve that fitting obtains, and Z is represented in pole plate positive active material PAM
PbO2Average content, σ represent the average response depth on electrode thickness direction, y0The coefficient that statistics calculates is represented, w represents weighting
Half peak breadth.
Anode plate described in above-mentioned technical proposal is discharged by different discharge electricity amounts, makes 40%, 50% respectively,
60%, 70%, 80%, 90%, each 1 of the anode plate of 100% 7 kind of different charging state.
After adopting the above technical scheme, the present invention has following positive effect:
(1) PbSO of the invention4It is larger with battery life relation to characterize the Main Ingredients and Appearance of pole plate, in test process,
Test draws the PbSO4 and PbO of each sample2Weight/mass percentage composition, by the reaction depth for determining plate active material PAM
Come the cycle life size of Pre-Evaluation battery and the quality of various products design, by the rate of change of reaction depth, really
The suitable depth of discharge of fixed all kinds of design batteries.
(2) present invention solves the problems, such as the analysis method of the active material of anode pole plate, by pole plate performance
Analysis and evaluation, depth of discharge, pole plate reaction depth and cycle life contrast, finds out optimal design, improves the cycle life of product,
Ensure product reliability and best use effect.
Embodiment
(embodiment 1)
The present invention is discharged positive electrode plate of lead-acid battery by different discharge electricity amounts, makes 40%, 50% respectively,
60%, 70%, 80%, 90%, each 1 of the anode plate of the different charging states such as 100%, represented successively with 1,2,3,4,5,6,7,
Every pole plate is divided into 5 layers along thickness d (mm) direction, per thickness degree be 0.2d (mm), in each layer between position sample, thickness sample
Point coordinates is 0.1d, 0.3d, 0.5d, 0.7d, 0.9d, the sample position in length and width direction in 0.25L~0.75L, 0.25B~
In the range of 0.75B, every layer is pressed upper, middle and lower, or left, center, right, samples at 3 points, and using after 3 sample mixeds as standard specimen,
Represented with -1, -2, -3, -4, -5, be numbered respectively by charging state and the number of plies respectively, as 4-3 represents the pole plate of charging state 70%
3rd layer of sample, samples taken carry out data processing with X-ray powder diffraction (XRD), and using Rietveld Refinement,
Draw the PbSO of each sample4And PbO2Weight/mass percentage composition.
Using gauss of distribution function to PbO2Content distribution curve be fitted, take
σ=2.25-w/2 (mm)
Wherein, A is the integral area for the Gaussian function curve that fitting obtains, and Z is represented in pole plate positive active material PAM
PbO2Average content, σ represents the average response depth on thickness direction, and y0 represents the coefficient that statistics calculates, and w represents weighting half
Peak width.By the rate of change of active material reaction depth, to characterize the optimal charging state of plate active material, (electric discharge is deep
Degree) or the charging performance of not plates of similar polarity it is good and bad.
Below by the A types using different designs scheme, Type B active substance for positive electrode of lead-acid accumulator PAM analyses test side
The embodiment of method, further illustrate present invention and its advantage.
1st, A types, Type B lead-acid accumulator sample are pressed into depth of discharge 0% respectively, 10%, 20%, 30%, 40%, 50%,
60% is discharged, and after electric discharge, the charging state of pole plate is respectively 100%, 90%, 80%, 70%, 60%, 50%, 40%.
2nd, A types, Type B lead-acid accumulator are dissected, samples pole plate and dry, every pole plate is identified, every pole plate
Upper point of 5 layers of sampling, every layer takes 3 samples, by upper, middle and lower, or left, center, right, samples at 3 points, and using after 3 sample mixeds as marking
Quasi- sample, it is numbered respectively by charging state and the number of plies, samples taken is analyzed with X-ray powder diffraction (XRD), and is utilized
Rietveld Refinement instruments carry out data processing, draw the PbO of each sample2Weight/mass percentage composition such as table 1, table
2。
Table 1 is A type battery difference charging state lower leafs PbO2Content, table 2 are Type B battery difference charging state lower leaf PbO2
Content.
Table 1
Table 2
Gauss of distribution function is adopted to the PbO under different charging states, different layers2Content distribution curve be fitted, with Z then
Represent PbO in pole plate positive active material PAM2Average content, σ represent thickness direction on average response depth, R represent intend
The confidence level of result afterwards, result is credible after this plan, such as table 3.
Table 3
3rd, variation tendency of the positive plate PAM reaction depths in discharge process is analyzed, contrast finds that A type battery charge states are
Reaction depth is 1.582 when 40% (depth of discharge 60%), reaction depth when charging state is 60% (depth of discharge 40%)
1.193, depth of discharge reduces 24.6%, and reaction depth rate of change is big, and depth of discharge is deepened, and empirically analyzes, and electric discharge is deep
Degree is deepened, and capacity attenuation can be accelerated, the fast prompt drop of cycle life.And Type B battery charge state is the anti-of 40% (depth of discharge 60%)
It is 1.202 to answer depth, and reaction depth 1.193 is close when with A types charging state be 60% (depth of discharge 40%), illustrates that Type B is electric
Pond remains to keep preferable cycle life under deeper depth of discharge 60%, can Pre-Evaluation go out the design of Type B battery and be better than A
Type.
1st, A types, the capacity attenuation speed of Type B battery and cycle life are analyzed
40%DOD discharge cycles standards are:
A) 0.1C puts 4h;
B) only, current limliting 0.25C fills 3h to 2.35V/;
C) continue a), b) step cycle 100 times;
D) circulate 100 times after terminating with 2.35V/cell, current limliting 0.2C charging 24h, charging
End carries out C10 capacity checks again;
E) a)~d is repeated) untill verification property capacity check is less than 80%C10.
60%DOD discharge cycles standards are:
A) 0.1C puts 6h;
B) only, current limliting 0.25C fills 5h to 2.35V/;
C) continue a), b) step cycle 100 times;
D) circulate 100 times after terminating with 2.35V/cell, current limliting 0.2C charging 24h, charging
End carries out C10 capacity checks again;
E) a)~d is repeated) untill verification property capacity check is less than 80%C10.
(1) capacity attenuation speed
A types battery puts capacity as initial capacity in fact when being recycled to the 500th time by depth of discharge 40%DOD circulations standard
99.2%, by depth of discharge 60%DOD circulation standard be recycled to the 500th time when put in fact capacity be initial capacity 87.5%, Type B
Battery puts 99.4% that capacity is initial capacity in fact when being recycled to the 500th time by depth of discharge 60%DOD circulations standard,
Experiment shows that A type battery discharge depth 40%DOD is circulated and Type B battery discharge depth 60%DOD, capacity attenuation
Speed is smaller, illustrates that A types battery is applied to 40% shallow circulation, Type B battery is applied to 60% deeper cavity.
(2) cycle life number
A type battery discharge depth 40%DOD cycle-indexes are 1800 times, and depth of discharge 60%DOD cycle-indexes only have
800 times, Type B battery discharge depth 60%DOD cycle-indexes are 1700 times, with A type battery discharge depth 40%DOD cycle-indexes
It is close.
Comprehensive depth of discharge, pole plate reaction depth and cycle life contrast, pole plate is anti-when A type battery discharges depth is 60%
It is 1.582 to answer depth, and pole plate reaction depth is 1.193 when depth of discharge is 40%, reduces 24.6%, corresponding cycle life
2.1 times are increased to, and pole plate reaction depth during Type B battery discharge depth 60% is 1.202, with A type battery discharge depth
Pole plate reaction depth 1.193 when 40% is close, and cycle life number is close.This explanation is by determining plate active material PAM
Reaction depth come the cycle life of Pre-Evaluation battery and the quality of various products design, pass through the change of reaction depth speed
Rate, design the suitable depth of discharge of battery.
Particular embodiments described above, the purpose of the present invention, technical scheme and beneficial effect are carried out further in detail
Describe in detail it is bright, should be understood that the foregoing is only the present invention specific embodiment, be not intended to limit the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., it should be included in the guarantor of the present invention
Within the scope of shield.
Claims (4)
1. a kind of active substance for positive electrode of lead-acid accumulator PAM analysis test methods, it is characterised in that comprise the following steps:
1) to the positive active material PAM Stratified Samplings of different charging states,
2) analyzed with X-ray powder diffraction,
3) data processing is carried out using Rietveld Refinement instruments,
4) PbSO of each sample is drawn4And PbO2Weight/mass percentage composition,
5) gauss of distribution function is adopted to the PbO under different charging states, different layers2Content distribution curve be fitted,
6) by the rate of change of active material reaction depth, to represent the depth of discharge of anode plate active material or not homopolarity
The charging performance of plate is good and bad.
2. active substance for positive electrode of lead-acid accumulator PAM analysis test methods according to claim 1, it is characterised in that:Institute
Stating step 1) is specially:The anode plate of lead-acid accumulator is discharged by the discharge electricity amount of different weight percentage, makes N respectively
The anode plate of the different charging states of kind, every kind of each 1, every pole plate is uniformly divided into 5 layers along thickness d direction, is per thickness degree
0.2d, in each layer between position sample, the sample position in length L directions is in 0.25L~0.75L, the sample position in width B directions
In 0.25B~0.75B, every layer is pressed upper, middle and lower, or left, center, right, samples at 3 points, and tried after 3 sample mixeds as standard
Sample, by charging state percentage, when the number of plies is numbered respectively.
3. active substance for positive electrode of lead-acid accumulator PAM analysis test methods according to claim 1, it is characterised in that:Institute
Stating step 5) is specially:Gauss of distribution function is adopted to PbO2Content distribution curve be fitted, take
σ=2.25-w/2 (mm)
<mrow>
<mi>Z</mi>
<mo>=</mo>
<mn>1</mn>
<mo>-</mo>
<mrow>
<mo>(</mo>
<msub>
<mi>y</mi>
<mn>0</mn>
</msub>
<mo>+</mo>
<mfrac>
<mi>A</mi>
<mn>4.5</mn>
</mfrac>
<mo>)</mo>
</mrow>
<mrow>
<mo>(</mo>
<mi>%</mi>
<mo>)</mo>
</mrow>
<mo>;</mo>
</mrow>
Wherein, A is the integral area for the Gaussian function curve that fitting obtains, and Z represents the PbO in pole plate positive active material PAM2
Average content, σ represent the average response depth on electrode thickness direction, y0The coefficient that statistics calculates is represented, w represents weighting half-peak
Width.
4. active substance for positive electrode of lead-acid accumulator PAM analysis test methods according to claim 2, it is characterised in that:Institute
State anode plate to be discharged by different discharge electricity amounts, make 40%, 50%, 60%, 70%, 80%, 90% respectively,
Each 1 of the anode plate of 100% 7 kind of different charging state.
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Cited By (2)
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CN109143082A (en) * | 2018-10-30 | 2019-01-04 | 双登集团股份有限公司 | The analysis of lead-acid accumulator optimal discharge depth test and appraisal procedure |
CN112305429A (en) * | 2020-09-28 | 2021-02-02 | 合肥国轩高科动力能源有限公司 | Estimation method for discharge depth of lithium ion battery |
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