CN105609781B - A kind of acid accumulator negative pole lead compound organic expander and preparation method thereof - Google Patents
A kind of acid accumulator negative pole lead compound organic expander and preparation method thereof Download PDFInfo
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- CN105609781B CN105609781B CN201510981606.2A CN201510981606A CN105609781B CN 105609781 B CN105609781 B CN 105609781B CN 201510981606 A CN201510981606 A CN 201510981606A CN 105609781 B CN105609781 B CN 105609781B
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- sodium lignosulfonate
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- composite material
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- humic acid
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- 239000002253 acid Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000002611 lead compounds Chemical class 0.000 title abstract description 4
- 229920005552 sodium lignosulfonate Polymers 0.000 claims abstract description 37
- 239000004021 humic acid Substances 0.000 claims abstract description 30
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 12
- 230000019635 sulfation Effects 0.000 abstract description 4
- 238000005670 sulfation reaction Methods 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052924 anglesite Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- 239000011505 plaster Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 239000004117 Lignosulphonate Substances 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 235000019357 lignosulphonate Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 229940068041 phytic acid Drugs 0.000 description 2
- 239000000467 phytic acid Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of acid accumulator negative pole lead compound organic expanders and preparation method thereof, and this approach includes the following steps：Sodium lignosulfonate and humic acid are mixed and are dissolved in water, initiator, crosslinking agent and acrylamide is added, graft copolymerization occurs, the compound organic expander is made.The composite material of sodium lignosulfonate and humic acid is made using graft copolymerization by the present invention, so that composite material is provided simultaneously with the excellent performance of the two, effectively extends the service life of accumulator；Composite material can effectively postpone sulfation compared with more active function groups that homogenous material has, and reduce internal resistance.
Description
Technical field
The present invention relates to lead-acid accumulator manufacturing technology fields, and in particular to a kind of acid accumulator negative pole lead is with compound organic
Swelling agent and preparation method thereof.
Background technology
Effect of the organic expander in negative plate mainly has at 2 points：First, preventing negative electrode active material in cyclic process
Surface area shrinkage, these materials can be adsorbed on electrode surface, so that maximum system energy is reduced by reducing surface tension；Second is that blunt
Change function, that is, influences the PbSO formed during negative discharge4Crystallization.
Cathode master organic expander to be used has sodium lignosulfonate and humic acid, the two to all have in lead accumulator at present
Identical active function groups can postpone negative plate passivation, improve negative electrode active material utilization rate, but to the influence of battery performance
It is different.It is well known that sodium lignosulfonate can effectively improve cold starting performance, extend discharge time, but of humic acid
Dynamic performance is relatively poor.Some researches show that, be used alone sodium lignosulfonate when, persistence is poor in cyclic process, solubility with
Temperature is increased and is dramatically increased, and easily by positive PbO2With the O in solution2Oxidation is decomposed and is lost；And humic acid is in the battery
When exclusive use, persistence is relatively good, is not susceptible to decompose, aoxidize or be lost.And many producers find to bear in plate and are added one
In use for some time, plate shelling is serious for quantitative sodium lignosulfonate, and sodium lignosulfonate leads to the probability of negative plate shedding
It is apparently higher than humic acid.So need to be in conjunction with the common characteristic of the two, preparation is conducive to extend battery discharge time, and persistence is good
Negative material.
Notification number is that the patent document of 101937996 B of CN discloses a kind of electric boosted automobile-used gelled lead acid battery
Cathode lead plaster and preparation method improve accumulator 2hr capacity, -15 DEG C of low temperature capacities and long-life for solving the problems, such as.The lead
Cream raw material contains the substance of following weight unit's：Lead powder 100, fiber 0.03~0.06, acetylene carbon black 0.1~0.5, barium sulfate
1.0~1.3, sodium lignosulfonate 0.1~0.2, humic acid 0.1~0.3, polyethylene glycol 0.1~0.3.Invention lead plaster synthesis wood
Plain sodium sulfonate low temperature ability is strong and feature that humic acid charge acceptance is strong, while in view of colloidal electrolyte uses, and
Polyethylene glycol is added in lead plaster raw material, the optimum proportioning of each constitutive material is determined by testing, forms a kind of novel cathode mixing
Organic expander ensure that 2hr capacity, -15 DEG C of low temperature capacities, cycle life, charge acceptance energy and the moisture content of accumulator are protected
The problem of holding ability, while also solving sodium lignosulfonate formula cryogenic property decaying.
Publication No. is that the patent document of 104659369 A of CN discloses a kind of preparation side of lead-acid battery modified lignosulphonate
Method is modified processing to sodium lignosulfonate.It is modified wood sodium have large specific surface area, be easily dispersed, wellability is good, low temperature inhale
It is attached, PH response ranges are wide, low PH adsorbances are high, slightly soluble in acid, to Pb2+The features such as strong adsorption.It is used as cathode additive agent,
Compared with slightly soluble lignin in existing acid, battery low temperature discharge capacity can be improved 20%；Heat-resisting quantity is strong, modified lignosulphonate collection normal wood
The best double advantages of plain microsolubility and before modified sodium lignosulfonate cryogenic property, are particularly suitable for that density of electrolyte is low, sour amount is big
Battery.
It is to improve plumbic acid in conclusion preparing performance more preferably negative material by being modified to organic swelling agent
The effective means of accumulator quality.
Invention content
The present invention provides a kind of acid accumulator negative pole lead compound organic expanders and preparation method thereof, altogether using grafting
The compound organic expander of cathode that can be reduced reaction resistance and extend discharge time is prepared in poly- reaction.
A kind of acid accumulator negative pole lead preparation method of compound organic expander, includes the following steps：By lignosulphonic acid
Sodium and humic acid mixing are dissolved in water, and initiator, crosslinking agent and acrylamide is added, graft copolymerization occurs, and are made described
Compound organic expander.
The characteristics of using sodium lignosulfonate and humic acid with acrylamide graft copolymerization occurs for the present invention, forms and combines
The composite material of sodium lignosulfonate and humic acid makes composite material both have the cold starting performance of sodium lignosulfonate, but also with
The characteristics of humic acid is not susceptible to decomposition, aoxidizes and be lost, battery life can be effectively improved by being applied in lead-acid accumulator.
Those skilled in the art can rationally adjust matching for sodium lignosulfonate and humic acid according to lead-acid accumulator actual demand
Than relationship, the present invention considers battery performance, it is desirable to increase the low temperature performance of battery.Preferably, the lignin sulphur
The weight ratio of sour sodium and humic acid is 3:1~4:1.
Preferably, the initiator is persulfate, such as ammonium ceric nitrate, potassium peroxydisulfate, ammonium persulfate.More preferably,
Initiator is ammonium persulfate.Because ammonium persulfate will not introduce other metal ions in the reaction, and when same initiation temperature,
The trigger rate of ammonium persulfate is very fast.
The effect of crosslinking agent is to generate chemical bond between the molecule of line style, and linear molecule is made to be connected with each other, and is formed
Reticular structure, improves the intensity of cross-linking products, and common crosslinking agent is polyethylene glycol, N-N '-methylene-bisacrylamides.As
It is preferred that the crosslinking agent is N-N '-methylene-bisacrylamides.
Preferably, the weight ratio of acrylamide and initiator is 100:1~200:1, the weight of acrylamide and crosslinking agent
Amount is than being 350:1~600:1.The weight ratio of the sodium lignosulfonate and acrylamide is 1:2.8~1:4.
Preferably, the temperature of the graft copolymerization is 40 DEG C~50 DEG C, the time is 4h~5h.
Preferably, above-mentioned preparation method further includes that reaction solution is added in isopropanol, standing separation sediment, washing is for several times
After dry.Addition isopropanol is compounded with after contributing to the precipitation of sediment, sediment to be washed for several times through ethyl alcohol up to the present invention
Machine swelling agent.
The present invention also provides the compound organic expanders of the acid accumulator negative pole lead made from above-mentioned preparation method.Research
It proves, relatively large number of active function groups is contained in compound organic expander prepared by the present invention, these functional groups are to lead ion
With very strong suction-operated, sulfation can be effectively postponed, reduces accumulator and reacts internal resistance；Compound organic expander energy
Falling off for active constituent in lead electrode is enough effectively reduced, the progress of charging reaction is conducive to；Compound organic expander can improve
The low temperature discharge capacity of battery.
The advantageous effect that the present invention has：(1) sodium lignosulfonate and humic acid is made using graft copolymerization in the present invention
Composite material, the excellent performance for making composite material both be provided simultaneously with effectively extends the service life of accumulator；(2) composite material
Compared with more active function groups that homogenous material has, sulfation can be effectively postponed, reduces internal resistance.
Description of the drawings
Fig. 1 is three kinds of material infrared spectrograms, and wherein a is humic acid, b is sodium lignosulfonate and c is composite material.
Fig. 2 is the AC impedance figure of lead electrode in different electrolytes, and wherein A is addition humic acid, B is addition lignosulphonic acid
Sodium, C are the composite material of the addition present invention, D is blank electrolysis liquid.
Fig. 3 is that lead electrode carries out the XRD diagram that 100 cyclic voltammetrics terminate rear surface in different electrolytes, and wherein A is to add
Humic acid, B is added to be addition sodium lignosulfonate, C is the composite material of the addition present invention, D is blank electrolysis liquid.
Fig. 4 is the discharge capacity test result figure under cryogenic of battery made from different materials, and wherein A1 is that addition is rotten
Phytic acid, B1 are addition sodium lignosulfonate, C1 is the composite material of the addition present invention, D1 is conventional batteries.
Specific implementation mode
With reference to embodiment and attached drawing, the invention will be further described.It is pointed out that embodiment described below
It is intended to be convenient for the understanding of the present invention, and does not play any restriction effect to it.Obvious those skilled in the art can be according to this
Various modifications and variations are made to the present invention in the range of text explanation, the model of the present invention is also included in these modifications and variations
In enclosing.
Embodiment 1
One, compound organic expander is prepared
Sodium lignosulfonate 1.5g is weighed, 100mL deionized waters, stirring is added in 250mL there-necked flasks in humic acid 0.5g
10min.Sequentially add 0.05g ammonium persulfates, 0.01gN-N '-methylene-bisacrylamides, 6g acrylamides, 40 DEG C of reaction 5h
Afterwards, brown solution is obtained.100mL isopropanols are added in solution, stand after a certain period of time, isolated sediment uses ethyl alcohol
Washing is for several times to get compound organic expander.
Two, material characterization
Humic acid, sodium lignosulfonate and above-mentioned composite material are subjected to infrared spectrum detection.The results are shown in Figure 1, and corruption is planted
Sour (a), sodium lignosulfonate (b) and composite material (c) have an absorption in each wave-length coverage, and composite material each wavelength have compared with
High absorption intensity.3400cm-1Left and right is the vibration absorption peak of-OH in carboxyl, 2930cm-1There is apparent absorption peak in left and right, is
The stretching vibration peak of methyl C-H, 1600~1770cm in methoxyl group-1Place be carboxyl in C=O stretching vibration peak, 1460~
1500cm-1Place and 1380cm-1It is nearby the flexural vibrations peak of C-H, 1100~1300cm-1It is C- to locate corresponding characteristic group
O.Within the scope of wavelengths above, 3 kinds of materials have absorption, illustrate to contain carboxyl or phenolic hydroxyl group, composite material in 3 kinds of materials
(c) because relative absorbance intensity is larger, corresponding functional group content is also higher.Sodium lignosulfonate (b) and composite material (c)
In, 1030~1040cm-1There is apparent absorption at place, is the stretching vibration peak of S=O, it may be possible to which the S=O double bonds in sulfonic group are said
Contain the identical functional group with sodium lignosulfonate (b) in bright composite material (c).From infrared spectrum analysis it is found that composite material (c)
In humic acid and sodium lignosulfonate be grafted, polymerize.
Three, performance detection
1, EIS is tested
0.02g humic acids (A), sodium lignosulfonate (B) and composite material (C) are dissolved in 100ml 0.1mol/L respectively
In NaOH solution, it is 1.34g/cm to be then added to density3System of the sulfuric acid solution as electrolyte, using stereotype as working electrode,
Mereurous sulfate is reference electrode, platinum electrode is to electrode, test each group electrochemical impedance value, and the NaOH that same amount is only added is molten
As a contrast for blank electrolysis liquid (D), the results are shown in Figure 2 for liquid.It is fitted each group impedance value using Zsimpwinnew softwares, such as
Table 1.
Table 1
Lead electricity in addition humic acid (A), sodium lignosulfonate (B), composite material (C) and blank electrolysis liquid (D) as shown in Table 1
Pole load transfer resistance sizes are respectively 75.57 Ω, 256.4 Ω, 74.49 Ω, 317 Ω.Blank electrolysis liquid D lead electrode load transfers resistance is most
Greatly, composite material C resistance minimums.The active function groups contained in the composite material known to infrared data are relatively more, and this
There are very strong suction-operated in a little functional groups to lead ion, and composite material is made more effectively to postpone sulfation, and internal resistance reduces.
2, XRD analysis
Lead electrode after being recycled 100 times during linear sweep voltammetry is tested is fixed on adhesive tape on sample cell, is used
XRD-6100 types X-ray diffractometer carries out material phase analysis to lead electrode surface, and CuK α, sweep speed are 0.02 (°)/s, step-length is
0.02 °, pipe presses 45kV, pipe stream 0.05A.The XRD diagram obtained to test with Jade5 softwares carries out composing fining fitting entirely, obtains
Pb and PbSO4Relative amount, in fit procedure, control least residue error (R) and estimation standard deviation (ESD) are respectively less than
10%.
The results are shown in Figure 3, and after electrode recycles 100 times in the electrolyte containing additive, there are Pb (corresponding marks on surface
Quasi- card：98-000-0279) and PbSO4(corresponding standard card number：It 98-00-0089) generates, but the corresponding peak position of each substance
It is equipped with offset, wherein after being recycled in the electrolyte C that composite material is added, the corresponding absorption peak peak type of lead electrode surface lead
It is relatively narrow, intensity is larger, illustrate that lead content is relatively more in active material.It is analyzed in conjunction with data fitting result it is found that rotten being added
Phytic acid, sodium lignosulfonate electrolyte A and B in recycle after, lead electrode surface lead relative amount is respectively 18.9%, 33.1%,
And after being recycled in the electrolyte C that composite material is added, lead electrode surface lead relative amount is about 40.3%, illustrates composite material
Addition be conducive to the progress of charging reaction,
Four, -18 DEG C of low temperature discharge capacities test of battery
Take humic acid (a), sodium lignosulfonate (b) and the composite material (c) of 0.2% (mass percent), respectively with
0.2% acetylene carbon black, 0.3% staple fiber, 0.5% barium sulfate, 99% lead powder (PbO contents 75%) mixing, by technique carry out with
Cream, smear, solidification, assembly and chemical conversion are assembled into finished product DZM-12 batteries, are denoted as A1, B1, C1, and conventional batteries are denoted as D1,
In, the content of a, b and c are identical as the total content of a and b in conventional batteries (D1).
The electric discharge of 100% depth of discharge (DOD) deeper cavity is carried out with ZS-110 high accuracy batteries test system, tests battery
Discharge performance in -18 DEG C of low temperature environments.Experimental procedure is：Stand 30min；Voltage is discharged to as 1.75V with 0.5C；It stands
30min；Voltage is charged to as 2.48V with 0.2C.
The results are shown in Figure 4, the battery B1 of addition sodium lignosulfonate (b), the discharge capacity highest at -18 DEG C, secondly
For the battery C1 of addition composite material (c), it is above the battery A1 for being individually added into humic acid (a) and conventional batteries D1 (humic acids
With the mechanical mixture of sodium lignosulfonate), illustrate that the addition of composite material (c) is conducive to improve the low temperature discharge capacity of battery.Knot
Close the interpretation of result of infrared spectrum and every electro-chemical test it is found that analysis the reason is that：Active function groups phase in composite material (c)
To more, pole plate internal driving is smaller, and electrode real table area is relatively large, advantageously forms short grained PbSO4, postpone pole
The passivation of plate improves low temperature discharge capacity.
Embodiment 2
Sodium lignosulfonate 2g is weighed, 100mL deionized waters, stirring is added in 250mL there-necked flasks in humic acid 0.5g
15min.Sequentially add 0.06g ammonium persulfates, 0.015gN-N '-methylene-bisacrylamides, 6.5g acrylamides, 45 DEG C of reactions
After 5h, brown solution is obtained.100mL isopropanols are added in solution, stand after a certain period of time, isolated sediment uses second
Alcohol washs for several times.
Embodiment 3
Sodium lignosulfonate 2.5g is weighed, 100mL deionized waters, stirring is added in 250mL there-necked flasks in humic acid 0.7g
20min.Sequentially add 0.07g ammonium persulfates, 0.02gN-N '-methylene-bisacrylamides, 7g acrylamides, 50 DEG C of reaction 5h
Afterwards, brown solution is obtained.100mL isopropanols are added in solution, stand after a certain period of time, isolated sediment uses ethyl alcohol
Washing is for several times.
Claims (4)
1. a kind of acid accumulator negative pole lead preparation method of compound organic expander, includes the following steps：By sodium lignosulfonate
It is dissolved in water with humic acid mixing, initiator, crosslinking agent and acrylamide is added, graft copolymerization occurs, is made described multiple
Close organic expander；
The weight ratio of the sodium lignosulfonate and humic acid is 3:1~4:1；
The weight ratio of the sodium lignosulfonate and acrylamide is 1:2.8~1:4；
The initiator is persulfate；
The crosslinking agent is N-N '-methylene-bisacrylamides；
The temperature of the graft copolymerization is 40 DEG C~50 DEG C, and the time is 4h~5h.
2. preparation method as described in claim 1, which is characterized in that the weight ratio of the acrylamide and initiator is 100:
1~200:1, the weight ratio of acrylamide and crosslinking agent is 350:1~600:1.
3. preparation method as described in claim 1, which is characterized in that including reaction solution is added in isopropanol, standing separation is heavy
Starch, washing are dried afterwards for several times.
4. the compound organic expander of acid accumulator negative pole lead made from the preparation method as described in claim 1-3 is any.
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