CN104505553B - A kind of lead-acid accumulator regenerated liquid concentrated solution and preparation method thereof - Google Patents
A kind of lead-acid accumulator regenerated liquid concentrated solution and preparation method thereof Download PDFInfo
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- CN104505553B CN104505553B CN201410689849.4A CN201410689849A CN104505553B CN 104505553 B CN104505553 B CN 104505553B CN 201410689849 A CN201410689849 A CN 201410689849A CN 104505553 B CN104505553 B CN 104505553B
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- 239000002253 acid Substances 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- -1 chlorobutylenes Chemical class 0.000 claims abstract description 6
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 5
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 5
- 229920013822 aminosilicone Polymers 0.000 claims abstract description 4
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims abstract description 4
- 239000011858 nanopowder Substances 0.000 claims abstract description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 11
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 2
- SMBGWMJTOOLQHN-UHFFFAOYSA-N lead;sulfuric acid Chemical compound [Pb].OS(O)(=O)=O SMBGWMJTOOLQHN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 6
- 238000012795 verification Methods 0.000 description 5
- 238000001994 activation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 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 3
- 229910052924 anglesite Inorganic materials 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010291 electrical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Secondary Cells (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
The present invention provides a kind of environmental protection lead-acid accumulator regenerated liquid concentrated solution and preparation method thereof.This regenerated liquid is made up of following percentage by weight proportioning component: Nano powder of silicon nitride 11～15%, poly-N vinyl pyrrolidone 0.1～0.15%, Polyethylene Glycol 0.2～0.25%, Na2OSiO210～20%, Na2SO41.2～1.8%, Na2CO31.0～1.5%, poly-3 chlorobutylenes 0.01～0.04%, poly-amino silicone 0.3～1.2%, nano-sized carbon 1～2%, Kaolin 0.3%～0.8%, surplus is water.The present invention can remove the lead sulfate crystallization on battery pole plates effectively; rational storage battery activation is coordinated to process; the capacity of lead acid battery through Regeneration Treatment is made to recover more than 95%; and protecting film is formed on battery pole plates surface; make battery pole plates no longer crystalline sulfuric acid lead, extend the service life of battery.
Description
Technical field
The present invention relates to battery technology field, be specifically related to a kind of lead-acid accumulator regenerated liquid and preparation method thereof.
Background technology
Lead-acid accumulator is a kind of standby energy being widely used in the fields such as communication, electric power, railway, traffic, and China is
Producing and use the big country of lead-acid accumulator, the yield of China's lead-acid accumulator in 2013 in the world is 205,027,428 kilovolt
Ampere-hour, increases by 15.36% on a year-on-year basis.The various accumulator that China scraps every year reach several hundred million, and annual rate of growth reaches 30%.Accumulator
Scrapping process is a global difficult problem, if it arbitrarily being abandoned, then environment can be produced huge pollution, directly endanger people
Class self.In world wide, in accumulator reparative regeneration field, the most do not find to enter commercial applications and the technology of popularization.
At present lead-acid accumulator is carried out regeneration method and mainly uses electrical method, including tandem reparation, large current charge reparation,
Negative pulse reparation, high-frequency impulse reparation etc..These methods are repaired lead-acid battery and be there is serious technological deficiency, mainly: 1, only
Can surface, part sulfuric acid of going crystallize；2, battery pole plates is caused major injury by big electric current, high voltage；3, can not be by sulfur
Lead plumbate crystallization reduction.Lead-acid accumulator after reparation quickly occurs that capacity declines and is quickly invalidated.Owing to it is the most really repaired
Battery, so above-mentioned various battery refresh methods cannot obtain promotion and application widely.
Summary of the invention
The primary and foremost purpose of the present invention is to propose a kind of lead-acid accumulator regenerated liquid concentrated solution, it is possible to effectively remove battery pole
Lead sulfate crystallization on plate, recovers capacity of lead acid battery, and forms protecting film on battery pole plates surface, make battery pole plates not
Recrystallization lead sulfate, extends the service life of battery.
The lead-acid accumulator regenerated liquid provided according to the present invention, is made up of the component of following components by weight percentage: receive
Rice beta-silicon nitride powder 11～15%, poly-N-vinyl pyrrolidone 0.1～0.15%, Polyethylene Glycol 0.2～0.25
%, Na2OSi02 10～20%, Na2SO41.2～1.8%, Na2CO31.0～1.5%, poly-3 chlorobutylenes 0.01～0.04%, poly-
Amino silicone 0.3～1.2%, nano-sized carbon 1～2%, Kaolin 0.3%～0.8%, surplus is water.
The lead-acid accumulator regenerated liquid concentrated solution that the present invention provides, coordinates deionized water to use, processes storage battery activation,
The lead sulfate crystalline solid being made waste and old lead acid accumulator polar board surface by the method for electrochemistry is softened, decomposes, is reduced into activity
Material, thus recover the capacity of lead-acid accumulator, reduce environmental pollution；Macromolecule organic material in inventive formulation exists
Thiazolinyl unsaturated group and hydroxyl, a portion hydroxyl is adsorbed on hydrophilic PbSO4 solid particle, and another part is hydrophilic
Hydroxyl be scattered in aqueous solution, form stable dispersion and do not coalesce, as the stabilizer in PbSO4 suspension and
Thickening agent, the stability of battery chemistries system is played an important role by these macromolecular materials；The height used due to the present invention
Including the ionic condition silicon of ultra-fine particles in molecular material, it acts on jointly with other polymer, add other from
Subconstiuent and the particle breakthrough of nano-sized carbon so that use the lead-acid accumulator of this regenerated liquid to possess higher electrical conductivity, permissible
Accept the impact of big electric current without generating heat, it is to avoid coming off further of active substance, extend the life-span of accumulator；The present invention's
The ultra-fine particles of battery refresh liquid is after discharge and recharge, and meeting formation one layer on each surface of electrolyte is the finest and close
Flexible colloidal thin film, can by the PbSO4 particle in battery chemistries system relatively securely in space orientation, from
And stop lead sulfate to crystallize.Penetrating plus nano-sized carbon so that these granules progressively decompose, and make existing knot on battery pole plates
Crystal is reduced by chemical reaction.
It is a further object to provide the preparation method of above-mentioned lead-acid accumulator regenerated liquid concentrated solution.
According to the preparation method of the lead-acid accumulator regenerated liquid concentrated solution that the present invention provides, load weighted raw material is placed in height
Means of press seals vessel in heating is to 100 DEG C～140 DEG C, and in high-pressure bottle, pressure reaches 40～70kg/cm2Time, keep some little
Time, then it is cooled to room temperature.
As preferred embodiment, the retention time is 24 hours.
It is a further object to provide a kind of lead-acid accumulator regenerated liquid, above-mentioned environmental protection lead-acid accumulator is regenerated
Concentrated liquor is mixed in the ratio of 1 to 99 with deionized water.
Detailed description of the invention
Below by the description to embodiment, the operation principle of the present invention and action effect etc. are made the most in detail
Explanation.
Embodiment 1:
Weigh raw material by weight percentage: Nano powder of silicon nitride 11～15%, poly-N-vinyl pyrrolidone 0.1
～0.15%, Polyethylene Glycol 0.2～0.25 %, Na2OSi02 10～20%, Na2SO41.2～1.8%, Na2CO31.0～
1.5%, poly-3 chlorobutylenes 0.01～0.04%, poly-amino silicone 0.3～1.2%, nano-sized carbon 1～2%, Kaolin 0.3%～
0.8%, surplus is water.Load weighted raw material is placed in high pressure sealing vessel in heating to 100 DEG C～140 DEG C, in high-pressure bottle
Pressure reaches 40～70kg/cm2Time, keep some hours, be then cooled to room temperature, obtain environmental protection lead-acid accumulator regenerated liquid dense
Contracting liquid.Lead-acid accumulator regenerated liquid concentrated solution is mixed in the ratio of 1 to 99 with deionized water, the lead acid storage battery being applied
Pond regenerated liquid.
Example effects:
Receiving 2 groups of 48V accumulator batteries, amount to 48 2V accumulator, model is soup shallow (YUASA) UXL-220-2N, mark
Capacity is called 220Ah；Being completely in the state of scrapping before reparation, discharge data is the most up to standard；
Carry out storage battery appearance inspection according to routine, the investigation work that record is done before reparation in accumulator, reject because of
The factor such as outward appearance, damage and do not possess repair be worth individuality.Through inspection, 48 single batteries without physical damage phenomenon,
Can repair；
Each single battery, the mode adding 1mL lead-acid accumulator regenerated liquid according to every AH, all add the ring of 220mL
Protect lead-acid accumulator regenerated liquid；
Whole accumulator are divided into 8 groups, often 6 single batteries of group, use the storage battery activation equipment of 12V, to 8 groups of storages
Battery activates；
In this batch of accumulator battery, the compliance rate that the first round is activated is 100%, and 8 groups the most up to standard, it is not necessary to carries out second and takes turns
Activation processes.
Validation verification:
The effectiveness repaired for checking storage battery activation, uses special discharge equipment to do verification property discharge test.With 24
Individual 2V single battery is one group, is divided into 2 groups, and testing standard is as follows:
First group uses 10C discharge rate, accumulator battery total voltage lower limit 43.2V, the configuration of monomer voltage lower limit 1.8V；
With discharge time as cut-off condition, detect conventional discharge application effect.
Second group uses self-defined verification discharge mode, accumulator battery total voltage lower limit 43.2V, monomer voltage lower limit
The configuration of 1.8V, detects the discharge capacity of accumulator battery with monomer voltage lower limit for electric discharge cut-off condition.
Accumulator battery electric discharge cut-off condition be arrive discharge time, any one single battery voltage is less than 1.8V, electric power storage
Pond group total voltage less than 43.2V three one of them.
Test result:
First group, it is set as 10C constant-current discharge.It is concluded that discharge time arrives, the battery discharging capacity of record is
219.385Ah, the 99.72%(for nominal are still above 1.8V due to whole single battery voltages, still have releasable space, reason
It is the discharge capacity requirement of satisfied 100% in opinion);
Second group storage battery group is to discharge according to the electric current of 10C discharge rate, and conclusion is that monomer voltage is less than 1.8V, note
The accumulator battery discharge capacity of record is 222.107Ah, is the 100.96% of accumulator battery nominal capacity.
Two group storage battery groups all use constant-current discharge pattern to carry out the electric discharge of verification property, according to electric discharge recording data, 2 groups of electric power storages
Verification property discharge data in pond is the most up to standard.
Claims (5)
1. a lead-acid accumulator regenerated liquid concentrated solution, it is characterised in that be made up of following percentage by weight proportioning component: nanometer
Beta-silicon nitride powder 11～15%, poly-N-vinyl pyrrolidone 0.1～0.15%, Polyethylene Glycol 0.2～0.25 %,
Na2OSi02 10～20%, Na2SO41.2～1.8%, Na2CO31.0～1.5%, poly-3 chlorobutylenes 0.01～0.04%, poly-ammonia
Radical siloxane 0.3～1.2%, nano-sized carbon 1～2%, Kaolin 0.3%～0.8%, surplus is water.
2. lead-acid accumulator regenerated liquid concentrated solution manufacture method described in a claim 1, it is characterised in that by load weighted former
Material is placed in high pressure sealing vessel in heating to 100 DEG C～140 DEG C, and in high-pressure bottle, pressure reaches 40～70kg/cm2Time, keep
Some hours, then it is cooled to room temperature.
Lead-acid accumulator regenerated liquid manufacture method the most according to claim 2, it is characterised in that the described retention time is 24
Hour.
4. a lead-acid accumulator regenerated liquid, it is characterised in that concentrated solution is mixed by the part by weight of 1 to 99 with deionized water
Forming, described concentrated solution is made up of following percentage by weight proportioning component: Nano powder of silicon nitride 11～15%, poly-N-second
Vinyl pyrrolidone 0.1～0.15%, Polyethylene Glycol 0.2～0.25 %, Na2OSi02 10～20%, Na2SO41.2～
1.8%, Na2CO31.0～1.5%, poly-3 chlorobutylenes 0.01～0.04%, poly-amino silicone 0.3～1.2%, nano-sized carbon 1～
2%, Kaolin 0.3%～0.8%, surplus is water.
Lead-acid accumulator regenerated liquid the most according to claim 4, it is characterised in that the insulation resistance of described deionized water is big
In 20M Ω.
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| CN201410689849.4A CN104505553B (en) | 2014-11-25 | 2014-11-25 | A kind of lead-acid accumulator regenerated liquid concentrated solution and preparation method thereof |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252748A (en) * | 2015-06-15 | 2016-12-21 | 何淑芳 | Lead-acid accumulator high-energy regenerated repair liquid |
| CN111029664B (en) * | 2019-12-13 | 2021-05-11 | 国网山东综合能源服务有限公司 | Lead storage battery regeneration liquid and preparation method and regeneration method thereof |
| CN113437372B (en) * | 2021-06-21 | 2023-04-25 | 河南润祥能源科技有限公司 | Repairing method and electrolyte for retired lead-acid battery and preparation method of repairing method and electrolyte |
| CN114171806B (en) * | 2021-12-01 | 2024-02-23 | 国网河北省电力有限公司电力科学研究院 | Active catalyst of lead-acid storage battery, lead-acid storage battery activator and preparation method of active catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101060178A (en) * | 2006-09-30 | 2007-10-24 | 冯艺峰 | An electrolytic liquid for manufacturing the electric medium of storage battery and its manufacture method |
| CN102709612A (en) * | 2012-05-14 | 2012-10-03 | 合肥佳联蓄能技术有限公司 | Repairing liquid of lead-acid storage battery |
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2014
- 2014-11-25 CN CN201410689849.4A patent/CN104505553B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101060178A (en) * | 2006-09-30 | 2007-10-24 | 冯艺峰 | An electrolytic liquid for manufacturing the electric medium of storage battery and its manufacture method |
| CN102709612A (en) * | 2012-05-14 | 2012-10-03 | 合肥佳联蓄能技术有限公司 | Repairing liquid of lead-acid storage battery |
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Address after: 403, building 5, building E, No. 510663, 3rd Street, Yushu Industrial Park, Guangzhou economic and Technological Development Zone, Guangdong, China Patentee after: GUANGZHOU HONGHUAI ENERGY TECHNOLOGY CO.,LTD. Address before: 403, building 5, building E, No. 510663, 3rd Street, Yushu Industrial Park, Guangzhou economic and Technological Development Zone, Guangdong, China Patentee before: GUANGZHOU HONGHUAI ELECTRONIC TECHNOLOGY Co.,Ltd. |
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Denomination of invention: A concentrated solution of lead-acid battery regeneration solution and its production method Effective date of registration: 20231128 Granted publication date: 20160921 Pledgee: Du Weiguang Pledgor: GUANGZHOU HONGHUAI ENERGY TECHNOLOGY CO.,LTD. Registration number: Y2023980068182 |
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Application publication date: 20150408 Assignee: Guangdong Tongshun Energy Technology Development Co.,Ltd. Assignor: GUANGZHOU HONGHUAI ENERGY TECHNOLOGY CO.,LTD. Contract record no.: X2024980001959 Denomination of invention: A concentrated solution of lead-acid battery regeneration solution and its production method Granted publication date: 20160921 License type: Exclusive License Record date: 20240205 |