CN105609781A - Composite organic expansive agent for negative electrode of lead-acid storage battery and preparation method of composite organic expansive agent - Google Patents
Composite organic expansive agent for negative electrode of lead-acid storage battery and preparation method of composite organic expansive agent Download PDFInfo
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- CN105609781A CN105609781A CN201510981606.2A CN201510981606A CN105609781A CN 105609781 A CN105609781 A CN 105609781A CN 201510981606 A CN201510981606 A CN 201510981606A CN 105609781 A CN105609781 A CN 105609781A
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- sodium lignosulfonate
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- 239000002253 acid Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title abstract description 35
- 239000003795 chemical substances by application Substances 0.000 title abstract description 10
- 229920005552 sodium lignosulfonate Polymers 0.000 claims abstract description 36
- 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 29
- 239000004021 humic acid Substances 0.000 claims abstract description 29
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000019635 sulfation Effects 0.000 abstract description 4
- 238000005670 sulfation reaction Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000003111 delayed effect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 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 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052924 anglesite Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011505 plaster Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000008961 swelling Effects 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229930188970 Justin Natural products 0.000 description 1
- 229920001732 Lignosulfonate Polymers 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000006071 cream 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
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 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
- 238000005259 measurement 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
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 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
- 238000006116 polymerization reaction Methods 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
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- -1 smear Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 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)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a composite organic expansive agent for a negative electrode of a lead-acid storage battery and a preparation method of a composite organic expansive agent. The method comprises the following steps of mixing and dissolving sodium lignosulphonate and humic acid in water; adding an initiator, a cross-linking agent and acrylamide; and carrying out graft copolymerization to prepare the composite organic expansive agent. According to the method, the graft copolymerization is used for preparing a composite material of the sodium lignosulphonate and the humic acid, so that the composite material simultaneously has favorable performance of the sodium lignosulphonate and the humic acid, and the service lifetime of the storage battery is effectively prolonged; and the composite material has more active functional groups than that of a single material, sulfation can be effectively delayed, and the internal resistance is reduced.
Description
Technical field
The present invention relates to lead-acid accumulator manufacturing technology field, be specifically related to the compound organic expander of a kind of acid accumulator negative pole leadAnd preparation method thereof.
Background technology
The effect of organic expander in negative plate mainly contains 2 points: the one, prevent negative electrode active material surface area in cyclic processShrink, these materials can be adsorbed on electrode surface, by reducing surface tension, maximum system energy are reduced; The 2nd, anti-deactivation function,Affect the PbSO forming in negative discharge process4Crystallization.
The organic expander that in lead accumulator, negative pole mainly uses at present has sodium lignosulfonate and humic acid, and the two all has identicalActive function groups, all can postpone negative plate passivation, improves negative electrode active material utilization rate, but on the impact of battery performance to some extent notWith. As everyone knows, sodium lignosulfonate can effectively improve cold starting performance, extends discharge time, but the starting performance of humic acidRelatively poor. There are some researches show, while using sodium lignosulfonate separately, in cyclic process, persistence is poor, solubility with temperature literHigh and significantly increase, and easily by anodal PbO2With the O in solution2Oxidation, decomposition and loss; And humic acid is independent in batteryWhen use, its persistence is relatively good, difficultly decomposes, oxidation or loss. And many producers find to add in negative plate a certain amount ofSodium lignosulfonate in use for some time, plate shelling is serious, sodium lignosulfonate causes the probability of negative plate shedding obviously highIn humic acid. So need, in conjunction with the two common characteristic, be prepared with and be beneficial to prolongation battery discharge time, and good negative pole of persistenceMaterial.
Notification number is that the patent documentation of CN101937996B discloses a kind of electric boosted automobile-used gelled lead acid battery negative electrode leadCream and preparation method, improve battery 2hr capacity ,-15 DEG C of low temperature capacity and long-life problem for solving. Described lead plaster raw materialThe material that contains 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, woodElement sodium sulfonate 0.1～0.2, humic acid 0.1～0.3, polyethylene glycol 0.1～0.3. The comprehensive sodium lignosulfonate low temperature of this invention lead plaster abilityStrong and the strong feature of humic acid charge acceptance considers that colloidal electrolyte uses simultaneously, and in lead plaster raw material, add poly-secondGlycol, by testing the best proportioning of determining each constitutive material, forms a kind of novel negative pole and is mixed with machine swelling agent, has ensured to holdPerformance and water retaining capacity are accepted in 2hr capacity ,-15 DEG C of low temperature capacity, cycle life, chargings of battery, have also solved simultaneouslyThe problem of sodium lignosulfonate formula cryogenic property decay.
Publication No. is the preparation method that the patent documentation of CN104659369A discloses a kind of lead-acid battery innovation wood sodium, to woodElement sodium sulfonate carries out modification. After modification wooden sodium have specific area large, be easy to disperse, wellability is good, cryogenic absorption, PHWide, the low PH adsorbance of response range is high, slightly soluble in acid, to Pb2+The features such as adsorptivity is strong. Use as cathode additive agent,Compared with slightly soluble lignin in existing acid, battery low temperature discharge capacity can improve 20%; Heat-resisting quantity is strong, innovation wood sodium collection normal woodTwo advantages of sodium lignosulfonate cryogenic property the best before element microsolubility and modification, are particularly useful for low, the sour amount of density of electrolyte largeBattery.
In sum, preparing the more excellent negative material of performance by organic swelling agent being carried out to modification, is to improve lead-acid accumulatorThe effective means of quality.
Summary of the invention
The invention provides a kind of compound organic expander and preparation method thereof for acid accumulator negative pole lead, utilize graft copolymerizationPrepare and can reduce reaction resistance, the compound organic expander of the negative pole that can extend again discharge time.
A preparation method for compound organic expander for acid accumulator negative pole lead, comprises the following steps: by sodium lignosulfonate and corruptionGrow acid mixing water-soluble, add initator, crosslinking agent and acrylamide, graft copolymerization occurs, described in making, be compounded withMachine swelling agent.
The present invention utilizes the feature of sodium lignosulfonate and humic acid and acrylamide generation graft copolymerization, forms in conjunction with lignin sulphurThe composite of acid sodium and humic acid, makes composite both possess the cold starting performance of sodium lignosulfonate, possesses again humic acid notEasily decompose, be oxidized and the feature of loss occurs, being applied in lead-acid accumulator and can effectively improving battery life.
Those skilled in the art can rationally adjust according to lead-acid accumulator actual demand the proportion relation of sodium lignosulfonate and humic acid,The present invention considers battery performance, wishes to improve the low temperature performance of battery. As preferably, described sodium lignosulfonate and corruptionGrowing sour weight ratio is 3:1～4:1.
As preferably, described initator is persulfate, as ammonium ceric nitrate, potassium peroxydisulfate, ammonium persulfate. More preferred, drawSending out agent is ammonium persulfate. Because ammonium persulfate can not introduced other metal ions in reaction, and when same initiation temperature, mistakeThe trigger rate of ammonium sulfate is very fast.
The effect of crosslinking agent is to produce chemical bond between the molecule of line style, and linear molecule is connected with each other, and forms netted knotStructure, the intensity of raising cross-linking products, conventional crosslinking agent is polyethylene glycol, N-N '-methylene-bisacrylamide. As preferably,Described crosslinking agent is N-N '-methylene-bisacrylamide.
As preferably, the weight ratio of acrylamide and initator is 100:1～200:1, and the weight ratio of acrylamide and crosslinking agent is350:1～600:1. The weight ratio of described sodium lignosulfonate and acrylamide is 1:2.8～1:4.
As preferably, the temperature of described graft copolymerization is 40 DEG C～50 DEG C, and the time is 4h～5h.
As preferably, above-mentioned preparation method also comprises isopropyl alcohol is added to reactant liquor, and standing separation sediment is dry after washing for several timesDry. Add isopropyl alcohol and contribute to sedimentary separating out, sediment obtains the compound organic expander of the present invention after ethanol washing for several timesAgent.
The present invention also provides the acid accumulator negative pole lead being made by above-mentioned preparation method compound organic expander. Studies have shown that,In compound organic expander prepared by the present invention, contain relatively many active function groups, these functional groups have very strong to lead ionSuction-operated, can effectively postpone sulfation, reduce battery reaction internal resistance; Compound organic expander can effectively subtractThe coming off of active component in few lead electrode, is conducive to the carrying out of charging reaction; Compound organic expander can improve the low temperature of batteryDischarge capacity.
The beneficial effect that the present invention possesses: (1) the present invention utilizes graft copolymerization to make the composite wood of sodium lignosulfonate and humic acidMaterial makes composite possess both premium properties simultaneously, effectively extends the life-span of battery; (2) composite is compared with homogenous materialThe more active function groups that have, can effectively postpone sulfation, reduce internal resistance.
Brief description of the drawings
Fig. 1 is three kinds of material infrared spectrograms, and wherein a is that humic acid, b are that sodium lignosulfonate and c are composite.
Fig. 2 is the AC impedance figure of lead electrode in different electrolytes, wherein A for add humic acid, B for add sodium lignosulfonate,C is that interpolation composite of the present invention, D are blank electrolysis liquid.
Fig. 3 is that lead electrode carries out 100 cyclic voltammetrics and finishes the XRD figure of rear surface in different electrolytes, and wherein A is for addingAdd humic acid, B for add sodium lignosulfonate, C for adding composite of the present invention, D is blank electrolysis liquid.
Fig. 4 is that the battery that different materials makes is transferred electric capacitance measurement test result figure at cryogenic conditions, wherein A1 for add humic acid,B1 is that interpolation sodium lignosulfonate, C1 are that interpolation composite of the present invention, D1 are conventional batteries.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described. It is pointed out that the following stated embodiment is intended to justIn the understanding of the present invention, and it is not played to any restriction effect. What obviously those skilled in the art can be according to explanation hereinIn scope, the present invention is made to various corrections and change, these corrections and change are also included in scope of the present invention.
Embodiment 1
One, prepare compound organic expander
Take sodium lignosulfonate 1.5g, humic acid 0.5g, in 250mL there-necked flask, adds 100mL deionized water, stirs 10min.Add successively 0.05g ammonium persulfate, 0.01gN-N '-methylene-bisacrylamide, 6g acrylamide, after 40 DEG C of reaction 5h,To brown solution. In solution, add 100mL isopropyl alcohol, leave standstill after certain hour, separate and be precipitated thing, wash with ethanolFor several times, obtain compound organic expander.
Two, material characterizes
Humic acid, sodium lignosulfonate and above-mentioned composite are carried out to infrared spectrum detection. Result as shown in Figure 1, humic acid (a),Sodium lignosulfonate (b) and composite (c) all have absorption in each wave-length coverage, and composite has higher absorption strong at each wavelengthDegree. 3400cm-1Left and right is in carboxyl-vibration absorption peak of OH, and 2930cm-1There is obvious absworption peak left and right, in methoxyl groupThe stretching vibration peak of methyl C-H, 1600～1770cm-1Place is the stretching vibration peak of C=O in carboxyl, 1460～1500cm-1PlaceAnd 1380cm-1Neighbouring is the flexural vibrations peak of C-H, 1100～1300cm-1Characteristic of correspondence functional group of place is C-O. More thanIn wave-length coverage, 3 kinds of materials all have absorption, illustrate in 3 kinds of materials and all contain carboxyl or phenolic hydroxyl group, and composite (c) is because phaseLarger to absorption intensity, so corresponding functional group content is also higher. In sodium lignosulfonate (b) and composite (c), 1030～1040cm-1There is obvious absorption at place, is the stretching vibration peak of S=O, may be the two keys of S=O in sulfonic group, and composite (c) is describedIn contain the functional group identical with sodium lignosulfonate (b). From infrared spectrum analysis, humic acid and lignin in composite (c), there is polymerization in sodium sulfonate grafting.
Three, Performance Detection
1, EIS test
0.02g humic acid (A), sodium lignosulfonate (B) and composite (C) are dissolved in respectively to 100ml0.1mol/LNaOH solutionIn, then to add density to be 1.34g/cm3Sulfuric acid solution is as the system of electrolyte, taking stereotype as working electrode, mereurous sulfate asReference electrode, platinum electrode are to electrode, test each group of electrochemical impedance value, only add the NaOH solution of same amount for blankIn contrast, result as shown in Figure 2 for electrolyte (D). Utilize the matching of Zsimpwinnew software respectively to organize resistance value, as table 1.
Table 1
Add as shown in Table 1 lead electrode load transfer in humic acid (A), sodium lignosulfonate (B), composite (C) and blank electrolysis liquid (D)Resistance sizes is respectively 75.57 Ω, 256.4 Ω, 74.49 Ω, 317 Ω. Blank electrolysis liquid D lead electrode load transfer resistance maximum, andComposite C resistance minimum. Relatively many by the active function groups containing in the known composite of infrared data, and these sensesThere is very strong suction-operated in group to lead ion, makes composite more can effectively postpone sulfation, and internal resistance reduces.
2, XRD analysis
The lead electrode adhesive tape circulating after 100 times in linear sweep voltammetry test is fixed on sample cell, uses XRD-6100Type X-ray diffractometer carries out material phase analysis to lead electrode surface, CuK α, sweep speed be 0.02 (°)/s, step-length be 0.02 °,Pipe is pressed 45kV, pipe stream 0.05A. The XRD figure that obtains of test is carried out to the matching that becomes more meticulous of full spectrum with Jade5 software, obtain PbAnd PbSO4Relative amount, in fit procedure, control least residue error (R) and estimation standard deviation (ESD) be all less than 10%.
As shown in Figure 3, electrode circulates after 100 times result in the electrolyte that contains additive, and all there is Pb (corresponding standard card on surfaceSheet: 98-000-0279) and PbSO4(corresponding standard card number: 98-00-0089) generates, but peak position corresponding to each material to some extentSkew, wherein, in the electrolyte C that adds composite after circulation, the plumbous corresponding absorption peak-to-peak type in lead electrode surface is narrower,Intensity is larger, illustrates that in active material, lead content is relatively many. Known in conjunction with data fitting interpretation of result, add humic acid,In the electrolyte A of sodium lignosulfonate and B, after circulation, the plumbous relative amount in lead electrode surface is respectively 18.9%, 33.1%, andAdd in the electrolyte C of composite after circulation, the plumbous relative amount in lead electrode surface is about 40.3%, and adding of composite is describedEnter to be conducive to the carrying out of charging reaction,
Four ,-18 of battery DEG C of low temperature discharge volume tests
Get humic acid (a), sodium lignosulfonate (b) and the composite (c) of 0.2% (mass percent), respectively all with 0.2% acetylene charcoalBlack, 0.3% short fiber, 0.5% barium sulfate, 99% lead powder (PbO content 75%) mix, and are undertaken and cream, smear, solid by techniqueChange, assemble and change into, be assembled into finished product DZM-12 battery, be designated as A1, B1, C1, conventional batteries is designated as D1, wherein,The content of a, b and c is identical with the total content of a in conventional batteries (D1) and b.
Carry out the dark circulation of 100% depth of discharge (DOD) with ZS-110 high accuracy battery test macro and discharge, test battery is at-18 DEG CDischarge performance in low temperature environment. Experimental procedure is: leave standstill 30min; Be discharged to voltage as 1.75V taking 0.5C; Leave standstill 30min;Charge to voltage as 2.48V taking 0.2C.
Result as shown in Figure 4, adds the battery B1 of sodium lignosulfonate (b), and the discharge capacity at-18 DEG C is the highest, secondly for addingAdd the battery C1 of composite (c), all higher than the battery A1 and conventional batteries D1 (humic acid and the lignin that add separately humic acid (a)The mechanical mixture of sodium sulfonate), illustrate and be conducive to improve the low temperature discharge capacity of battery adding of composite (c). In conjunction with infrared spectrumAnd the interpretation of result of every electro-chemical test is known, analysis reason is: in composite (c), active function groups is relatively many, pole plateInternal driving is less, and electrode real surface is long-pending relatively large, is conducive to form short grained PbSO4, postpone the passivation of pole plate,Improve low temperature discharge capacity.
Embodiment 2
Take sodium lignosulfonate 2g, humic acid 0.5g, in 250mL there-necked flask, adds 100mL deionized water, stirs 15min.Add successively 0.06g ammonium persulfate, 0.015gN-N '-methylene-bisacrylamide, 6.5g acrylamide, after 45 DEG C of reaction 5h,Obtain brown solution. In solution, add 100mL isopropyl alcohol, leave standstill after certain hour, separate and be precipitated thing, wash with ethanolWash for several times.
Embodiment 3
Take sodium lignosulfonate 2.5g, humic acid 0.7g, in 250mL there-necked flask, adds 100mL deionized water, stirs 20min.Add successively 0.07g ammonium persulfate, 0.02gN-N '-methylene-bisacrylamide, 7g acrylamide, after 50 DEG C of reaction 5h,To brown solution. In solution, add 100mL isopropyl alcohol, leave standstill after certain hour, separate and be precipitated thing, wash with ethanolFor several times.
Claims (9)
1. a preparation method for compound organic expander for acid accumulator negative pole lead, comprises the following steps: by sodium lignosulfonate andHumic acid mixes water-soluble, adds initator, crosslinking agent and acrylamide, and graft copolymerization occurs, and makes described compoundOrganic expander.
2. preparation method as claimed in claim 1, is characterized in that, the weight ratio of described sodium lignosulfonate and humic acid is3:1～4:1。
3. preparation method as claimed in claim 1, is characterized in that, described initator is persulfate.
4. preparation method as claimed in claim 1, is characterized in that, described crosslinking agent is N-N '-methylene-bisacrylamide.
5. preparation method as claimed in claim 1, is characterized in that, the weight ratio of described sodium lignosulfonate and acrylamide is1:2.8～1:4。
6. preparation method as claimed in claim 1, is characterized in that, the weight ratio of described acrylamide and initator is100:1～200:1, the weight ratio of acrylamide and crosslinking agent is 350:1～600:1.
7. preparation method as claimed in claim 1, is characterized in that, the temperature of described graft copolymerization is 40 DEG C～50 DEG C,Time is 4h～5h.
8. preparation method as claimed in claim 1, is characterized in that, comprises isopropyl alcohol is added to reactant liquor, and standing separation is heavyShallow lake thing, dry after washing for several times.
9. the compound organic expander of acid accumulator negative pole lead that as described in as arbitrary in claim 1-8, preparation method makes.
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