CN1274960A - Maitenance-free colloid accumulator and its making process - Google Patents

Abstract

The colloid accumulator has positive and negative plates of Pb-Ca-Al-Sn alloy containing Pb 99.7-99.8wt%, Ca 0.08-0.10 wt%, Al 0.01-0.02 wt% and Sn 0.10-0.15 wt% and colloid electrolyte compounded with silica sol in 45-50 vol% and sulfuric acid in 50-55 vol% as well as auxiliary colloid electrolyte material H3O4 in 1-2 wt%. The colloid electrolyte has high gas-separating overvoltage and less self-discharge to ensure the lasting and stable operation of the accumulator. In certain pressure, gas can reach plate via pores in colloid electrolyte to re-compound into water inside the accumulator. With less or no maintenance, the accumulator may be used widely.

Description

A kind of maitenance-free colloid accumulator and preparation method thereof

The invention belongs to field of chemical power source, specifically, is a kind of maitenance-free colloid accumulator and preparation method thereof.

As everyone knows, as the colloid storage battery of one of maintenance-free lead accumulator kind,, be widely used socially because it has characteristics such as acid nonleakage, battery life length.And along with studying extensively and profoundly, its electric property constantly obtains to improve.

In the colloid storage battery research field, the maximum of people report are colloidal electrolytes.

Patent CN1065557 has set forth the colloidal electrolyte of A agent and B agent formation.Wherein the A agent contains Ludox, deionized water, cleanser, and the B agent contains bright sulfur acid, deionized water, cleanser.Enumerated a large amount of cleansers in the patent, and utilized the storage battery self discharge of this colloidal electrolyte perfusion little, the energy transformation ratio height still can keep heavy-current discharge at 50 ℃.

Patent CN1084319 has emphasized a kind of glue electrolyte for lead acid accumulator, is by sulfuric acid, Ludox, and alkali metal (Li, Na, K) hydroxide solution constitutes.Battery capacity after the can is all above existing national standard.

Patent CN2045148 has invented a kind of colloidal electrolyte of high-capacitance.Contain Ludox (SiO ₂3-9.9%), sulfuric acid (48.1-75%), sulfuric acid/silicon dioxide (g/g) is than being 4.5-10.5.In colloidal electrolyte, contain 0.1-0.5 aluminium hydroxide, capacitance is increased.This patent statement the method is cheap, superior performance, and technology is simple.

Patent CN1036479 use purity as the high purity water of 5-15 megaohm to industrial metasilicate with 10-12: after 1 part by weight carries out dissolved dilution,, add an amount of pure Na of analysis through positive anion exchange resin process ₂SiO ₃9H ₂O is as stabilizer, concentrates after making pH value reach 12-14, and obtaining proportion is 1.075-1.099, contains SiO ₂Weight ratio is 11.7-15%, Na ₂The O weight ratio is 0.26-0.35%, and pH value is the silica gel agent of 12-14.Storage battery with this glue perfusion meets national standard.

Suchlike report is a lot of.But the battery service workload that obtains with these colloidal electrolyte perfusions is bigger, especially restive to the moisturizing process.If moisturizing is too much, sulfuric acid density descends in the electrolyte, influences electric property and not by the excessive water that colloid absorbed, still is being with acidity to be free in the outside, and it still can produce the sour phenomenon of overflowing, and has lost " solid dielectric " meaning; If moisturizing very little, colloidal electrolyte can dry up and battery capacity be put to come out cause end-of-life.In addition, being optimized combination from the battery each several part, to improve the electric report of overall performance that waits of colloid storage battery considerably less.

One of purpose of the present invention is by optimizing each parts of colloid storage battery to improve the electric overall performance of colloid storage battery.

Two of purpose of the present invention provides a kind of making superior performance, the colloid storage battery manufacture method that cost is moderate.

Technical scheme of the present invention is achieved in that a kind of maitenance-free colloid accumulator, it mainly comprises housing, be contained in the housing with just, the pole plate group that negative plate combines, align with bus-bar, negative plate is spliced, just, accompany dividing plate between the negative plate and form single lattice, battery cover and housing seal, the leading-out end of bus-bar from battery cover just, draw in the negative terminal hole, just refill, negative terminal, safety valve is equipped with at battery cover place at housing, the colloid dielectric is housed in housing, it is characterized in that: this just, negative plate is the alloy of Pb-Ca-Al tin, its percentage by weight is that Pb accounts for 99.7-99.8%, Ca accounts for 0.08-0.10%, and Al accounts for 0.01-0.02%, and Sn accounts for 0.10-0.15%; The colloid dielectric is that Ludox 45-50% and sulfuric acid 50-55% are formulated preferably with thixotropic property, and the auxiliary H that adds the 1-2% of colloid dielectric quality ₃PO ₄

A kind of manufacture method of maitenance-free colloid accumulator, it comprises by positive plate, negative plate makes the pole plate group, and electric dividing plate and pole plate group make single lattice, more single lattice are seated in the battery case, make storage battery and adopt epoxy that fat is sealed then.To inject in the sealed cell by the colloidal electrolyte that Ludox, sulfuric acid are made into, make colloid storage battery, check finished product to dispatch from the factory through initial charge with after safety valve being installed within it again, it is characterized in that:

(a) the big 5-10% of rated capacity of pole plate group's Capacity Ratio battery;

(b) Ludox that adopts in the colloid dielectric is to be concentrated to proportion after sodium metasilicate exchanges through positive negative resin to be: 1.058-1.060g/cm ³(20 ℃), specific area are 200-250m ²/ g contains SiO ₂9-11%, Fe＜0.001%, Cl＜0.001% stabilizer 2-3%;

(c) to join 50-55 part proportion be 1.45-1.55g/cm to the 1-2% phosphoric acid of colloid dielectric weight ³In the sulfuric acid, stir evenly at normal temperatures:

(d) get sulfuric acid and each portion of silicon sol solution that contains phosphoric acid, mixing and stirring injecting accumulator.

The present invention has very high gassing overpotential because pole plate is adopted Pb, Ca, Al, Sn as grid alloy, can reduce self discharge, realizes sealing, contains SiO in the dividing plate ₂Can improve this dividing plate compatibility between job stability and solid dielectric in battery more than 45%, and reduce internal resistance; It is 200-250m that dielectric adopts specific area ²/ g, the siloxane solvent of grain through being evenly distributed and sulfuric acid match and form.Can make H ₂SO ₄It is well-balanced and stable to distribute in medium, and concentration stratification phenomenon can not occur, and an even property of particle diameter makes battery operated stable, lasting simultaneously; The unidirectional valve that employing is opened in the certain pressure scope automatically, can be implemented in certain pressure therapeutic method to keep the adverse qi flowing downward body and can arrive pole plate by colloid dielectric microporous network, be combined into water again, realize the circulation of water and the circulation of oxygen at inside battery, reduced the loss of water, reached and realize non-maintaining purpose.This colloid storage battery after tested with application, stable performance, capacity is big, self discharge is little, can be widely used in occasions such as post and telecommunications, ups power system, sedan limousine, train, ships and electric power system.

Fig. 1 is the colloid storage battery structural representation among the present invention

Fig. 2 is the colloid storage battery manufacture method block diagram among the present invention

The invention will be further described and provide embodiment for following condensation accompanying drawing

Maitenance-free colloid accumulator among the present invention mainly comprises housing 1, be contained in the housing by positive plate 2, the pole plate group that combines of negative plate 3, with bus-bar 4 align, negative plate splices, just, Accompany dividing plate 5 between the negative plate, and can form some single lattice according to battery capacity, battery cover 6 and housing 1 Sealing, the leading-out end of bus-bar 4 is drawn from the terminals 7 of battery cover, and is interior near battery cover 6 places at housing 1 Safety valve 8 is housed, fills colloid dielectric 9 in housing 1, it is different from prior art and is: this is positive and negative Pole plate adopts the Pb-Ca-Al ashbury metal, and its percentage by weight is: Pb accounts for 99.7-99.8%, and Ca accounts for 0.08-0.10%, Al accounts for 0.01-0.02%, and Sn accounts for 0.10-0.15%; The colloid dielectric is with thixotroping The 45-50% Ludox of better performances, formulated with the sulfuric acid of 50-55%, and the auxiliary colloid electricity that adds The H of the 1-2% of medium-weight percentage₃PO ₄COSO with 0.05-0.2%₄ The specific area of Ludox is 200-250m²/ g contains SiO₂9-11% contains Fe less than 0.001%, contains Cl less than 0.001%, and pH value is 8-10; Dividing plate contains SiO₂Be more than 45%, aperture≤8um, porosity 〉=60%, resistance≤300m Ω; Shell Body 1 interior safety valve 8 near the battery cover place adopts check valve, and the automatic opening pressure of this check valve is 10-25KPa. A kind of preparation method of maitenance-free colloid accumulator is different from prior art and is: positive and negative Pole plate adopts the Pb-Ca-Al ashbury metal, and its percentage by weight is that lead accounts for 99.7-99.8%, and calcium accounts for 0.08-0.10%, aluminium accounts for 0.01-0.02%, and tin accounts for 0.10-0.15%. Hold according to the battery of making Amount decides the required pole plate number of every single lattice, specific algorithm to be, the capacity of battery is divided by every pole plate The number that obtains behind the capacity adds 1, is required positive plate number, and the negative plate number adds 1 for the positive plate number. Such as system Make 100Ah, every pole plate capacity is 18Ah, and then required positive plate number is 100/18=5.6, gets 5 and adds 1 is 6, thus adopt 6 positive plates and 7 negative plates, with the specified appearance of the Capacity Ratio battery that guarantees the pole plate group Measure big 5-10% and contain SiO with inserting between the positive and negative pole plate₂Be more than 45%, aperture≤8um, porosity 〉=60%, in the battery jar of packing into behind the dividing plate of resistance≤300m Ω; With epoxy resin battery is sealed Get up, adopt air gauge to detect monomer after 24 hours and whether leak, not leak to qualified; The colloid electricity is situated between The Ludox that adopts in the matter is to be concentrated to proportion after the sodium metasilicate process sun resistance resins exchange to be 1.058-1.060g/cm³(20 ℃), specific area are 200-250m²/ g contains SiO₂9-11%, Fe≤0.001%. Cl≤0.001%, stabilizing agent 2-3%; The 1-2% phosphoric acid of colloid dielectric weight is added Be 1.45-1.55g/m to 50-55 part proportion²In the sulfuric acid, stir evenly at normal temperatures: get the sulphur that contains phosphoric acid Acid stirs well even injecting accumulator with each portion of silicon sol solution: poured into the battery of colloidal electrolyte through quiet Put after 4 hours and carry out initial charge, initial charge divides two stages, and every one-phase is extremely every with the 0.1C current charges Use the 0.05C current charges instead behind single lattice 2.45V, extremely end in constant 3 hours behind every single lattice 2.75V. Leave standstill 2 Hour or longer after with the 0.1C current discharge till every single lattice 1.75V, second stage holding after for discharge Battery is added the every single lattice 2.45V of constant voltage behind the colloidal electrolyte of identical proportion, with the 0.4C current charges Till dropping to 0.001C to electric current, the amount of electrolyte after adding is 12-15ml/Ah; Fill after charging electricity It is the check valve of 5-20KPa that good safety valve, this safety valve adopt automatic opening pressure, can realize this The colloid storage battery of bright made.

Provide embodiment below

Embodiment 1:12V-FMJ-100Ah colloid storage battery

Every 18Ah of positive and negative electrode alloy: Pb (99.8%) Ca (0.08%) Al (0.02%) Sn (0.10%), every single lattice be with 13 assemblings, totally 6 single lattice; Dividing plate adopts the SWP dividing plate, and safety valve adopts the VENTSEAL2000 type glue valve of German Bao Se company, opens automatically under 20KPa.

Colloidal electrolyte is to be 1.058g/cm with proportion ρ ³(our company produces the Ludox of (20 ℃) voluntarily, and its specific area is 205m ²/ g) with ρ be 1.53g/cm ³It is 1.29g/m that the sulfuric acid solution equal-volume of (20 ℃) is mixed into ρ ³(20 ℃) poured into storage battery in 2 hours.Wherein, the auxiliary phosphoric acid (weight ratio) that adds WT:1%.Leave standstill charging after 1 hour.Charging divides two stages, is that 10A is charged to that to use 20 hour rates behind the 14.7V instead be that 5A charges to behind the 16.5V and finishes after constant 3 hours with 10 hour rate currents.Adopting 10 hour rates is that the 10A electric current discharges, and finishes after voltage is 10.5V.Discharge capacity is 101Ah.Add isopycnic colloidal electrolyte liquid after the discharge, carry out the second time fully.At this moment, always add liquid measure and reach 13ml/Ah.Charging for the second time adopts constant voltage 14.7V all to fill.At first adopt the 40A charging, charging finishes when electric current is reduced to 0.1A.Safety valve is installed, is covered gland, clean warehouse-in.This battery is tested after testing, and capacity 10 hour rates can reach 103Ah, are higher than set quota.

The self discharge test: putting preceding 10 hour rate capacity in storage is 104Ah (25 ℃), charging back warehouse-in.Entry time is on September 29th, 1997, and the outbound time is on July 19th, 1998.Under 25 ℃, discharge with 10 hour rates.Discharge capacity is 78.5Ah.Resting period length is 290 days.Self-discharge rate every day is (103-78.5) ÷ 290 ÷ 103 * 100%=0.082%.

Embodiment 2:2V-FMJ-300Ah colloid storage battery

Every 34Ah of positive and negative pole plate alloy: Pb (99.75%) Ca (0.085%) Al (0.015%) Sn (0.15%), every single lattice are with 21 assemblings: dividing plate adopts the PVC-2000 type; The one-way cock opening pressure that adopts is 13KPa;

Colloidal electrolyte is to be 230m with the specific area ²/ g Ludox and ρ are 1.45g/m ³The sulfuric acid solution of (20 ℃) is in the V Ludox: it is 1.27g/m that V acid=45: 55 ratios are mixed into ρ ³(20 ℃) poured into storage battery in 2 hours.Wherein, the phosphoric acid (weight ratio) of auxiliary adding 1%.Leave standstill charging after 2 hours.Charging divides two stages, is that 30A is charged to that to use 20 hour rates behind the 2.45V instead be that 15A charges to behind the 2.75V and finishes after constant 3 hours with 10 hour rate currents.Adopting 10 hour rates is that the 30A electric current discharges, and finishes after voltage is 1.75V.Discharge capacity is 310Ah.Add isopycnic colloidal electrolyte liquid after the discharge, carry out the charging second time.At this moment, always add liquid measure and reach 14ml/Ah.Charging for the second time adopts constant voltage 2.45V all to fill.At first adopt the 120A charging, charging finishes when electric current is reduced to 0.3A.Safety valve is installed, is covered gland, clean warehouse-in.This battery is tested through test, and capacity 10 hour rates can reach 315Ah, are higher than set quota.

Self discharge test: press the method for embodiment 1, recording self-discharge rate every day is 0.076%.

Embodiment 3:12V-FMJ-10AH colloid storage battery

Every 2.8AH of positive and negative electrode alloy: Pb (99.78%) Ca (0.09%) Al (0.01%) Sn (0.12%); 4 of every single lattice positive plates; Negative 5 assemblings of plate, totally 6 single lattice, dividing plate is adopted the material with SUP, and safety valve adopts example 1 material.Being controlled at 25Kpa opens down automatically.

The colloid dielectric is 1.058g/cm with ρ ³(our company produces the Ludox of (20 ℃) voluntarily, and its specific area is 245m ²/ g) with ρ be 1.55g/cm ²It is 1.30g/m that the sulfuric acid solution of (20 ℃) is made into ρ by equal-volume ³(20 ℃); Wherein auxiliary 2% the phosphoric acid that adds colloid dielectric total weight pours into battery and charging after static 1 hour.Charging divides two stages, and being charged to cell voltage with the 1.5A constant current is to use the 0.5A charging instead behind the 14.7V, after final voltage rises to 16.8V, and 3 hours voltage constants complete charge then.Behind 10.5V, finish (discharge capacity is 10.3Ah) with the 1A current discharge.Then add isopycnic colloidal electrolyte liquid, carry out the second time fully.At this moment, adding up to add liquid measure is 12ml/Ah.Charging for the second time adopts constant voltage 14.7V all to fill.Being charged to electric current with 2A reduces to voluntarily and spends 3 hours behind the 0.1A and finish.Safety valve is installed, is cleaned, cover gland.This battery testing situation: 10 hour rate capacity: 10.4Ah; 10A discharge: 31min; Self-discharge rate every day is 0.09%; Sealed reaction efficient: 98% (pressing the JB/T64572-92 method).

Claims (5)

1. maitenance-free colloid accumulator.It mainly comprises housing, be contained in the pole plate group who combines with the positive and negative electrode newspaper in the housing, with bus-bar align, negative plate splices, between positive and negative pole plate, accompany dividing plate and form single lattice, battery cover and housing seal, the leading-out end of bus-bar is drawn from the positive and negative terminal hole of battery cover, refills positive negative terminal and at the battery cover place of housing safety valve is housed.The colloid dielectric is housed in housing, it is characterized in that: the alloy of this positive and negative pole plate lead, calcium aluminium tin.Its percentage by weight is: Pb accounts for 99.7-99.8%, and Ca accounts for 0.08-0.10%, and Al accounts for 0.01-0.02%, and Sn accounts for 0.10-0.15%; The colloid dielectric is that Ludox 45-50% and sulfuric acid 50-55% are formulated preferably with thixotropic property, and the auxiliary H that adds the 1-2% of colloid dielectric weight ₃PO ₄

2. by the described a kind of maitenance-free colloid accumulator of claim 1, it is characterized in that: the specific area of Ludox is 200-250m ²/ g; Contain SiO ₂9-11% contains Fe less than 0.001%, contains Cl less than 0.001%, and pH value is that the proportion of 8-10 sulfuric acid is 1.45-1.55g/cm ³

3. by claim 1 or 2 described a kind of maitenance-free colloid accumulators, it is characterized in that: dividing plate contains SiO ₂Be more than 45%, aperture≤8um, porosity 〉=60%, resistance≤300m Ω.

4. by claim 1 or 2 described a kind of maitenance-free colloid accumulators, it is characterized in that: near the safety valve at battery cover place, adopt unidirectional valve in the housing, the automatic opening pressure of this unidirectional valve is 10-25KPa.

5. the manufacture method of a maitenance-free colloid accumulator.It comprises by positive plate, negative plate makes the pole plate group, make single lattice by dividing plate and pole plate group, again single lattice are seated in the battery case, making storage battery adopts epoxy resin to seal then, to inject by the colloidal electrolyte that Ludox, sulfuric acid are made in the sealed cell, make colloid storage battery, check finished product to dispatch from the factory through new charging with after safety valve being installed within it again, it is characterized in that:

(a) the big 5-10% of rated capacity of pole plate group's Capacity Ratio battery;

(b) Ludox that adopts in the colloid dielectric is to be concentrated to proportion after sodium metasilicate exchanges through positive negative resin to be: 1.058-1.060g/cm ³(20 ℃), specific area are 200-250m ²/ g contains SiO ₂9-11%, Fe＜0.001%, Cl＜0.001% stabilizer 2-3%;

(c) to join 50-55 part proportion be 1.45-1.55g/cm to the 1-2% phosphoric acid of colloid dielectric weight ³In the sulfuric acid, stir evenly at normal temperatures:

(d) get sulfuric acid and each portion of silicon sol solution that contains phosphoric acid, mixing and stirring injecting accumulator.

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