CN105845930A - Preparation method of positive activated material for energy storage lead-carbon battery - Google Patents
Preparation method of positive activated material for energy storage lead-carbon battery Download PDFInfo
- Publication number
- CN105845930A CN105845930A CN201610307250.9A CN201610307250A CN105845930A CN 105845930 A CN105845930 A CN 105845930A CN 201610307250 A CN201610307250 A CN 201610307250A CN 105845930 A CN105845930 A CN 105845930A
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- Prior art keywords
- lead
- energy storage
- preparation
- carbon battery
- activating substance
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
-
- 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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a positive activated material for an energy storage lead-carbon battery. The activated material is mainly prepared by dry mixing, wet mixing and acid mixing of multiphase lead oxide, a polypropylene fiber and a composite additive; firstly, basic lead sulphate seed crystal, tin oxide, antimony oxide and graphene are mechanically premixed at a certain ratio to prepare the composite additive; then mixing reaction is carried out; and the temperature is controlled at 55-80 DEG C in the preparation process. The prepared activated material is high in adhesion, high in utilization rate and good in conductivity, is used for manufacturing the energy storage lead-carbon battery; the charge acceptance and the over-discharge capacity can be obviously improved; and the POSC cycle lifetime can be obviously prolonged.
Description
Technical field
The present invention relates to a kind of polar plate of lead acid storage battery full-filling material, particularly energy storage lead carbon battery positive pole activating substance
Preparation method.
Background technology
Solar photovoltaic technology, wind technology development increasing to the effect of human society, special Shi Fei developed country,
In outlying district, the situation of electricity shortage.Although solar photovoltaic, wind energy resources are abundant, but owing to the collection of solar energy, wind energy fills
Put and energy storage battery mainly uses flow battery, colloid flooded batteries energy storage, use input cost, working service cost
Of a relatively high, hinder the development of solar energy, wind technology.International community advocates thriftiness the energy in recent years, it is achieved recycling economy,
The development advancing battery energy storage technology is imperative, and solving energy storage technology is solar energy, the key of wind technology development.Due to
At present energy storage scene uses environment poor, battery often in overcharging or charge less state, lead-acid battery is just proposed by this
Higher requirement.Lead carbon battery is a kind of lead-acid battery adding material with carbon element compound additive in the electrodes, and performance has and significantly carries
High.This type of battery active mass existing and the adhesion of grid, charging utilization rate are the highest, and active material electric conductivity is poor, uncomfortable
Overcharge or charge less state for being in, cause shorter battery life, it is impossible to meet solar energy, wind energy storage battery uses requirement,
Energy storage cost is the highest, constrains the development and progress of solar energy, wind technology.
Summary of the invention
The technical problem to be solved in the present invention is the weak point overcoming existing lead acid battery positive electrode activating substance, it is provided that
A kind of adhesion is strong, charging utilization rate height, good conductivity, mistake high temperature resistant, resistance to are put, the energy storage lead carbon battery positive pole of resistance to charge less is lived
The preparation method of compound matter.
The technical scheme is that the preparation method of energy storage lead carbon battery positive pole activating substance, heterogeneous lead is aoxidized
Thing, polypropylene fiber, compound additive be dry mixed 10～15 minutes, adds deionized water wet mixing 5～10 minutes, adds dilute sulfuric acid
Acid is mixed makes for 15～20 minutes, its improvements be described heterogeneous lead oxides be lead monoxide, brown lead oxide, metal free lead
Mixture, each Ingredient percent is: metal free lead 10%～15%, lead monoxide 30%～35%, brown lead oxide 50%～
60%, the component of described compound additive and mass percent are basic lead sulphate crystal seed 25%～30%, tin oxide 25%～45%,
Antimony oxide 25%～35%, graphite dilute 5%～10%, the addition of described polypropylene fiber and compound additive accounts for the oxidation of heterogeneous lead respectively
The 0.3%～0.5% of material amount.
Further scheme is: first by basic lead sulphate crystal seed, tin oxide, antimony oxide, Graphene by proportioning at 25 DEG C～
Carry out carrying out again after machinery premixing forms compound additive the preparation of activating substance at a temperature of 35 DEG C.
Deionized water temperature used is 20 DEG C～30 DEG C, and the percent concentration of dilute sulfuric acid is 35%～50%, activating substance system
During Bei, temperature controls at 55 DEG C～80 DEG C.
The addition of deionized water used and dilute sulfuric acid accounts for the 8%～11% and 6%～9% of heterogeneous lead oxides quality respectively.
In the present invention, add basic lead sulphate crystal seed and favorably improve the discharge and recharge formation effect of battery, make lead plaster metallographic group
Knit uniformly, add tin oxide and favorably improve charge acceptance, add antimony oxide and solve non-antimony effect and over-discharge performance, add
Enter Graphene and improve the activity of positive pole pole material, electric conductivity, improve and recharge recovery capability during circulating battery, go from
The addition of sub-water has reduced, and the density of sulfuric acid increased and consumption reduces beneficially change lead plaster metallurgical structure.
Formula materials is pre-mixed, the favourable uniformity improving pole plate component and chemical reaction uniformity, preparation process keeps
Suitable temperature is also sequentially added into, and is effectively improved the structure of active material, suppresses battery dehydration, improves battery charging by energy
Power, overdischarge ability, extend the cycle life of battery.
Detailed description of the invention
The present invention and beneficial effect thereof is further illustrated below by embodiment.
Example 1, the positive pole activating substance component of example 2 and content are following (in table, numeral is mass percent):
In upper table, the mass percent of compound additive each component is basic lead sulphate crystal seed 26%, tin oxide 41%, antimony oxide
26%, Graphene 7%,
Its preparation method is: be first 25 in temperature by a certain percentage by basic lead sulphate crystal seed, tin oxide, antimony oxide, Graphene
DEG C～35 DEG C at carry out machinery premixing formed compound additive, multiplex lead oxides use high temperature melting, gaseous oxidation legal system
Making, the component of its lead powder is free lead according to a certain ratio, lead monoxide, brown lead oxide, then by heterogeneous lead oxides, compound
Additive, polypropylene fiber stir mixing 10 minutes by proportioning under dry state, more at the uniform velocity add deionization in 5 minutes
Water, continues stirring 9 minutes, adds sulfuric acid, acid addition time 12 minutes, continues stirring 8 minutes, make positive pole activating substance.System
Controlling during Bei and cream temperature is at 55～80 DEG C, when going out cream smear, temperature controls 55～65 DEG C.
Process of the test and the effect of the present invention described below:
1, prepared by battery
Positive pole activating substance described in example 1 makes positive plate, and technique assembles and makes HL-500 energy storage lead carbon battery 16 routinely
Only, with 10hr calculation of capacity, prepared anode activating substance dry weight is 16.0g/Ah, and negative active core-shell material dry weight is
12.2g/Ah.With 1.22g/ml(25 DEG C) sulfuric acid (after adding a certain proportion of sulfate) to battery acid filling, in chemical conversion uses
Chemical conversion five is filled three and is put standard, after battery rolls off the production line, stands 48 hours, and the pressure reduction 35mV that discharges by measure, terminal voltage 10mV carry out combo.
From 16 sample, extract 12 be made into 2 groups, be circulated life test respectively, then take out 2 and be charged ability to accept test,
2 carry out over-discharge ability test.Detection equipment uses 48V300A type battery circulating inspector and discharge and recharge instrument.
2, charge acceptance test
Sample Cell extracts 2 batteries, respectively with 50A current discharge 5h, places into 25h in the low temperature chamber of 0 DEG C, take out
In 1min, with the charging of constant voltage 2.35V, battery is charged, after 10min, records maximum charging current and be respectively
157A, 160A, the battery maximum charging current of prior art is typically at about 100A, and the present invention improves the charging of battery and is subject to
Ability.
3, over-discharge ability
From Sample Cell extract 2 batteries, after fully charged in the environment of 20 DEG C～25 DEG C with I10 current discharge to connecing
Nearly 0V, short circuit 24h, then fill 48h with 2.35V/ monomer constant voltage and current limiting I10 and then carry out C10 capacity check, it is carried out continuously 8 times and follows
After ring, the reality of battery 1 puts 101.8% that capacity is initial capacity (C10 when 25 DEG C), and it is initial that the reality of battery 2 puts capacity
The 102.5% of capacity (C10 when 25 DEG C).And the battery of routine techniques only has about 90%, over-discharge ability significantly improves.
4, POSC 20%-80% cycling life test
2 Battery packs (often group 6) that will prepare, carry out being circulated life test, experimental enviroment under normal temperature, high temperature respectively
For: test at normal temperature 25 DEG C for the 1st group, test at high temperature 45 DEG C for the 2nd group.
Circulation standard is:
A) 0.2C puts 1h；
B) 0.19C puts 3h；
C) only, current limliting 0.2C fills 3h to 2.35V/；
D) continue b), c) step cycle 100 times；
E) with 2.35V/cell after circulation terminates for 100 times, current limliting 0.15C charging 24h, charging terminates to carry out C10 capacity inspection again
Survey；
F) a)-e is repeated) till verification property capacity check is less than 60%C10.
(1) capacity attenuation speed
Normal temperature is tested: when battery pack 1 is recycled to the 500th time, capacity is the 100.5% of initial capacity, and decay, is not recycled to 1000
Being the 99% of initial capacity time secondary, capacity has only decayed 3%.
High temperature test: when battery pack 2 is recycled to the 500th time, capacity is the 101% of initial capacity, decay, is not recycled to
Being the 98.7% of initial capacity when 1000 times, capacity has only decayed 5%.
Time the circulating battery of prior art is to 500 times, capacity attenuation about 15% during cold test, when hot test
Capacity attenuation about 30%, it can be seen that, the capacity attenuation speed of the present invention is obviously reduced, and high temperature resistant cycle performance has had substantially
Improve.
(2) cycle life number of times
Being circulated by above-mentioned cycle life standard, the discharge capacity of whole Battery pack is stopped, at normal temperature when being less than the 60% of rated capacity
Under environment, the cycle-index of (the 1st group) is 2400 times, and (the 2nd group) is 1500 times in high temperature environments.The battery of prior art is normal
Cycle-index typically only about 1000 times under temperature environment, cycle-index typically only about 600 times under hot environment.
Can illustrate from above-mentioned result of the test, use the battery charging that example 1 gained activating substance of the present invention makes by energy
Power, overcharging resisting power, normal temperature, high-temperature cycle life performance significantly improve.
The battery using example 2 gained activating substance of the present invention to make carries out above-mentioned test, also obtains same effect.
Claims (4)
1. an energy storage preparation method for lead carbon battery positive pole activating substance, by heterogeneous lead oxides, polypropylene fiber, compound adds
Add agent to be dry mixed 10～15 minutes, add deionized water wet mixing 5～10 minutes, add dilute sulfuric acid acid and mix 15～20 minutes systems
Become, it is characterized in that described heterogeneous lead oxides is lead monoxide, brown lead oxide, the mixture of metal free lead, each composition quality
Percentage is: metal free lead 10%～15%, lead monoxide 30%～35%, brown lead oxide 50%～60%, described compound additive
Component and mass percent be: basic lead sulphate crystal seed 25%～30%, tin oxide 25%～45%, antimony oxide 25%～35%, stone
Ink dilute 5%～10%, the addition of described polypropylene fiber and compound additive account for respectively heterogeneous lead oxides quality 0.3%～
0.5%。
2. as described in claim 1 energy storage by super lead carbon battery positive pole activating substance preparation method, it is characterised in that first by alkali
Formula lead sulfate crystal seed, tin oxide, antimony oxide, Graphene carry out machinery premixing at a temperature of 25 DEG C～35 DEG C by proportioning and are formed multiple
The preparation of activating substance is carried out again after closing additive.
3. the energy storage preparation method of lead carbon battery positive pole activating substance as described in claim 1, it is characterised in that spent from
Sub-coolant-temperature gage is 20 DEG C～30 DEG C, and the percent concentration of dilute sulfuric acid is 35%～50%, and in activating substance preparation process, temperature controls
At 55 DEG C～80 DEG C.
4. the energy storage preparation method of lead carbon battery positive pole activating substance as described in claim 1, it is characterised in that spent from
The addition of sub-water and dilute sulfuric acid accounts for the 8%～11% and 6%～9% of heterogeneous lead oxides quality respectively.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610307250.9A CN105845930B (en) | 2016-05-11 | 2016-05-11 | The preparation method of energy storage lead carbon battery anode activating substance |
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| CN201610307250.9A CN105845930B (en) | 2016-05-11 | 2016-05-11 | The preparation method of energy storage lead carbon battery anode activating substance |
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| CN105845930A true CN105845930A (en) | 2016-08-10 |
| CN105845930B CN105845930B (en) | 2018-07-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107492632A (en) * | 2017-08-02 | 2017-12-19 | 双登集团股份有限公司 | Delay the method for process for positive slab lattice of lead-acid accumulator corrosion rate |
| CN109192988A (en) * | 2018-10-26 | 2019-01-11 | 漳州市华威电源科技有限公司 | A kind of lead-acid battery positive electrode active material additive and preparation method thereof |
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| CN101841029A (en) * | 2010-05-20 | 2010-09-22 | 江苏双登集团有限公司 | Cathode active material of lead-acid battery for UPS (Uninterruptible Power Supply) |
| CN102244248A (en) * | 2011-06-10 | 2011-11-16 | 江苏双登集团有限公司 | Positive plate of lead storage battery for electric bicycle |
| CN102664256A (en) * | 2012-04-27 | 2012-09-12 | 天能电池集团有限公司 | Anode lead plaster of power lead-acid storage battery polar plate |
| CN102903932A (en) * | 2012-10-18 | 2013-01-30 | 双登集团股份有限公司 | Lead-acid storage battery positive electrode plate for electric automobile |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101841029A (en) * | 2010-05-20 | 2010-09-22 | 江苏双登集团有限公司 | Cathode active material of lead-acid battery for UPS (Uninterruptible Power Supply) |
| CN102244248A (en) * | 2011-06-10 | 2011-11-16 | 江苏双登集团有限公司 | Positive plate of lead storage battery for electric bicycle |
| CN102664256A (en) * | 2012-04-27 | 2012-09-12 | 天能电池集团有限公司 | Anode lead plaster of power lead-acid storage battery polar plate |
| CN102903932A (en) * | 2012-10-18 | 2013-01-30 | 双登集团股份有限公司 | Lead-acid storage battery positive electrode plate for electric automobile |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107492632A (en) * | 2017-08-02 | 2017-12-19 | 双登集团股份有限公司 | Delay the method for process for positive slab lattice of lead-acid accumulator corrosion rate |
| CN107492632B (en) * | 2017-08-02 | 2019-11-19 | 双登集团股份有限公司 | Delay the method for process for positive slab lattice of lead-acid accumulator corrosion rate |
| CN109192988A (en) * | 2018-10-26 | 2019-01-11 | 漳州市华威电源科技有限公司 | A kind of lead-acid battery positive electrode active material additive and preparation method thereof |
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| CN105845930B (en) | 2018-07-17 |
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