CN105895918A - Negative electrode active material additive for lead storage battery - Google Patents
Negative electrode active material additive for lead storage battery Download PDFInfo
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- CN105895918A CN105895918A CN201410773476.9A CN201410773476A CN105895918A CN 105895918 A CN105895918 A CN 105895918A CN 201410773476 A CN201410773476 A CN 201410773476A CN 105895918 A CN105895918 A CN 105895918A
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- lead
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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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Abstract
The invention belongs to the technical field of material synthesis and energy, and particularly relates to a negative electrode additive for a lead storage battery and a preparation method. Laminated carbon is deposited on a potassium carbonate or sodium carbonate substrate through vapor deposition; and a lead nitrate solution and a sulfuric acid solution are successively added to generate a laminated carbon/lead sulfate composite material in situ. When the obtained composite material is taken as the negative electrode active material additive for a lead-acid storage battery, the battery has high specific capacity and excellent cycling stability and rate capability, and is expected to be applied to a high-energy density, high-power density and long-lifetime lead-acid battery as the negative electrode additive.
Description
Technical field
The present invention relates to a kind of lead-acid battery anode additive and preparation method, belong to materials synthesis and energy technology field.
Background technology
Along with traditional fossil energy day is becoming tight, and environmental pollution is serious all the more, seeks the approach of sustainable development, conservation of nature
Resource and natural environment become the serious challenge of 21 century.The large-scale application of the generation of electricity by new energy mode such as wind energy, solar energy is not from
Open energy storage system, the storage of electric energy, convert, carry and all use battery/capacitance technology.
Electric automobile (including pure electric vehicle EV and hybrid electric vehicle HEV) reduces pollution and use cost is low, is expected to adjust
The paddy electricity at humorous network system night, becomes current study hotspot and the development trend of future transportation instrument.
Lead battery because its raw material resources are abundant, cheap, the feature such as preparation, service procedure be ripe and safety is good, no matter
It is to store up electricity on a large scale, or in electric motor car, has preferable application prospect.But its specific power is low at present, cycle life is short
Shortcoming can not meet currently the most growing to power source performance demand.Ultracapacitor (Supercapacitors) be performance between
A kind of Novel energy storage apparatus between traditional capacitor and battery, its specific energy is 20～200 times of traditional capacitor, specific power one
As more than 1000W/kg, higher than general secondary cell, cycle life (＞ 105Secondary) also superior to battery, also there is energy moment big
Current charge-discharge electricity, operating temperature range width, the advantage such as safe and pollution-free, thus have on electric automobile latent before application
Scape.But, up to now, the specific energy of electrochemical capacitor, again below secondary cell, constrains its answering in electric motor car
With.
The specific power of lead battery is relatively low and the high power discharge lower life-span is poor, is mainly limited to negative pole: put at high-density current
In the case of electricity, negative pole produces a large amount of lead ions and enters electrolyte, and situation on the other side is that in electrolyte, sulfate ion diffusion is subject to
Limit, causes lead ion supersaturation, easily forms one layer of fine and close lead sulfate beds of precipitation in negative terminal surface, cause negative terminal surface to be passivated.
Lead sulfate poorly conductive, dissolubility is little, can reduce the reactivity of the internal lead of negative pole, increases reaction overpotential, when causing charging
Liberation of hydrogen is more serious, and charge efficiency declines, and forms vicious cycle.If continuing high-power discharge and recharge, case above can be further
Deteriorating, lead sulfate precipitation granule increases and process is irreversible, and final negative pole loses reactivity, and battery failure (sees J.Power
Sources 133(2004)126).If can be by the control of external circuit, it is to avoid the high-power discharge and recharge of lead battery, can be effectively improved
Its life-span.Chinese patent 200620097371.7 discloses a kind of battery, and it is one resistance to high power in traditional battery loong shunt
The capacitor of discharge and recharge, is fixed battery and electric capacity by a shell, constitutes a kind of battery-capacitor combination.Such battery-electricity
Although holding combination lead battery and ultracapacitor to be combined, but belonging to outer combination type, two power supplys are required to respective
Electrolyte, barrier film etc., not only device cumulative volume is bigger, in addition it is also necessary to external circuit and corresponding management system carry out real-time testing, control
System, cost relatively office.
If " the most also " of ultracapacitor Yu lead battery being made into " the most also ", then can save external circuit and the control system of complexity,
Effectively reduce cost.Chinese patent 200810136333.1 discloses a kind of lead battery, and it is carbon plate institute that its part bears level stereotype
Replace, lead battery specific power can be improved, extend battery life.Chinese patent 200910002836.4 discloses super electricity
Container activated carbon electrodes and the battery of lead negative pole " the most also ", the most also have people referred to as " superbattery " (Ultrabattery, ginseng
See J.Power Source 174 (2007) 16).This battery by the high-specific-power of ultracapacitor, long-life blend of predominance to lead
In accumulator, while keeping improving power, prolongation battery life advantage, circuit can be simplified again, improve specific capacity, and drop
Low total cost (sees " the science news commentary " special column in " science Times " on August 14th, 2009).But, owing to decreasing negative pole
Sheet, the specific energy of this battery will decline.
Super-activated carbon is added directly in negative plate of lead storage battery, also can well play the effect promoting battery impulse power.
As the openest in Chinese patent 200810136333.1, Chinese patent 200880009193.X and Chinese patent 200910098917.9
Activated carbon is directly added into lead-acid battery electrode plate, can be effectively improved device performance.It addition, Chinese patent 2012102068940
Also the CNT of polymolecularity, grapheme material are done additive, it is possible to be effectively improved lead battery the pulse cycle life-span and
Charge acceptance.
But, activated carbon, CNT and Graphene can make the cost of battery improve as additive, and carbonaceous material can accelerate
The liberation of hydrogen effect of battery.Therefore, utilize cheap raw material and technique to prepare the material with carbon element of high connductivity, and In-situ reaction presses down thereon
The compound of liberation of hydrogen processed and the composite prepared as the cathode additive agent of lead-acid battery, a kind of solve having of the problems referred to above by being
Efficacious prescriptions method.
Summary of the invention
It is an object of the invention to provide a kind of negative plate of lead storage battery additive, the energy density of lead battery, power can be improved close
Degree and service life cycle.
Technical scheme is as follows:
The preparation method of cathode additive agent, specifically comprises the following steps that
(1) putting in reactor by catalyst substrate, temperature is 500～890 DEG C；Then being passed through flow in reactor is
5～500ml/min carbon sources are reacted, and the response time is 0.5～1000min, catalyst surface deposition on or superscribe stratiform
Carbon-coating, obtain complex；
(2) complex of step (1) gained successively adds 0.01～2mol/L lead nitrate solution, 0.01～10mol/L sulfuric acid solution to enter
Row reaction, products therefrom carries out filtering, cleaning, and i.e. obtains the carbon/lead sulfate composite of stratiform after drying at 60～250 DEG C；
Catalyst substrate described in step (1) be potassium carbonate, sodium carbonate more than one, carbon source be methane, methanol, acetylene, ethanol,
More than one in benzene, toluene, bad hexane, acetonitrile, phthalocyanine.
Composite of the present invention, on the evengranular lamella being distributed in carbon of lead sulfate, the number of plies of carbon is 1～50 graphite linings, long
Degree and width are 10nm～1cm × 10nm～1cm, and the size of lead sulfate granule is 5nm～200nm.Stratiform carbon and the weight of lead sulfate
Amount ratio is 1: 1～200.This composite is as 0.01～5% that additive addition is aluminum accumulator negative plate active substance quality.
The feature of composite additives to negative electrodes prepared by the present invention is: the stratiform carbon part of this additive provides bigger specific surface
Long-pending, beneficially lead sulfate granule dispersed provide the express passway of electric transmission, improve the electron conduction of negative pole.
Lead sulfate is evengranular to be distributed on carbon-coating, it is suppressed that the liberation of hydrogen of carbon, also makes composite become strong with the binding ability of lead plaster.
Composite additives has bigger compacted density, it is easy to uniformly mix with lead plaster；The stratiform carbon of high conductivity and nanometer sulphuric acid
The combination of the excellent structure of the evengranular distribution of lead, the sulfation produced when being discharged by anticathode plays inhibitory action.And
And, the preparation process price of composite is low, easy and simple to handle, easy industrialization.
Beneficial effects of the present invention: apply this composite as negative electrode active material additive, the negative pole of lead battery can be made
The contrast of active substance specific energy is not added with the battery of this additive and improves 10～35%, and power density improves 20～30%, and circulation makes
More than 30% is improved with the life-span.
Detailed description of the invention
Embodiment 1
With potassium carbonate as substrate, toluene is carbon source, and the flow being passed through is 200ml/min, reaction in-situ after 700 DEG C of deposition 1h
Generate stratiform carbon/lead sulfate composite.This composite laminate carbon is 1: 20 with the weight ratio of lead sulfate, the length of stratiform carbon
Degree and width are all between 10 μm～100 μm, and the number of plies is 20～40 layers.In a lead battery negative electrode active material,
Add battery 10 hour rate of this compound additive of 1% mass ratio, 2 hour rate specific discharge capacities are respectively 169.0mAh/g
And 137.3mAh/g, it is respectively increased 18.3% and 30.3% than the capacity of blank battery respective rate electric discharge.And 2 hour rates
After 100 circulations, battery capacity conservation rate is 92%, and after 100 circulations of blank battery, capacity is reduced to the 80% of initial capacity
Below.
Embodiment 2
With potassium carbonate as substrate, toluene is carbon source, and the flow being passed through is 200ml/min, the most anti-after 700 DEG C of deposition 20min
Stratiform carbon/lead sulfate composite should be generated.This composite laminate carbon is 1: 50 with the weight ratio of lead sulfate, stratiform carbon
Length and width is all between 10 μm～100 μm, and the number of plies is 5～20 layers.In a lead battery negative electrode active material,
Add the battery 10C electric discharge duration of this compound additive of 2% mass ratio more than 220 seconds；Under high magnification partial state of charge
The cycle-index of (HRPSoC, the mode charge and discharge cycles of 2C electric discharge 60S after using 2C charging 90S) can reach 53000
Secondary, hence it is evident that to be better than blank battery (10000～20000 times).
Embodiment 3
With sodium carbonate as substrate, toluene is carbon source, and the flow being passed through is 300ml/min, the most anti-after 700 DEG C of deposition 30min
Stratiform carbon/lead sulfate composite should be generated.This composite laminate carbon is 1: 10 with the weight ratio of lead sulfate, stratiform carbon
Length and width is all between 1 μm～30 μm, and the number of plies is 10～30 layers.In a lead battery negative electrode active material,
Add battery 10 hour rate of this compound additive of 1% mass ratio, 2 hour rate specific discharge capacities are respectively 166.0mAh/g
With the cycle-index of 135.7mAh/g, HRPSoC can reach 46000 times.
Embodiment 4
With potassium carbonate and sodium carbonate mixed in equal amounts as substrate, methane is carbon source, and the flow being passed through is 200ml/min, sinks at 780 DEG C
After long-pending 40min, reaction in-situ generates stratiform carbon/lead sulfate composite.This composite laminate carbon with the weight ratio of lead sulfate is
1: 40, the length and width of stratiform carbon is all between 1 μm～100 μm, and the number of plies is 10～40 layers.At a lead battery
In negative electrode active material, add the battery 10C electric discharge duration of this compound additive of 4% mass ratio more than 240 seconds；HRPSoC,
Cycle-index can reach 48000 times.
Embodiment 5
With potassium carbonate as substrate, acetonitrile is carbon source, and the flow being passed through is 200m]/min is the most anti-after 700 DEG C of deposition 40min
Stratiform carbon/lead sulfate composite should be generated.This composite laminate carbon is 1: 30 with the weight ratio of lead sulfate, stratiform carbon
Length and width is all between 10 μm～100 μm, and the number of plies is 10～50 layers.In a lead battery negative electrode active material,
Add the circulation that battery 2 hour rate specific discharge capacity is 139.8mAh/g, HRPSoC of this compound additive of 3% mass ratio
Number of times can reach 44000 times.
Claims (2)
1. a lead battery negative electrode active material additive, it is characterized in that: this additive is carbon and lead sulfate composite, wherein carbon is 100～2.0 with the mass ratio of lead sulfate, on the evengranular lamella being distributed in carbon of nano-sulfur lead plumbate, the number of plies of carbon is 1～50, length and width is 10nm～1cm × 10nm～1cm, and the size of lead sulfate granule is 5nm～200nm, and this additive addition is the 0.01～5% of negative plate of lead storage battery active substance quality；Nano-sulfur lead plumbate granule is 1.0～150nm.
2. the preparation method of composite negative electrode active material additive as claimed in claim 1, it is characterised in that this preparation method specifically comprises the following steps that
(1) putting in reactor by catalyst, temperature is 500～890 DEG C；Then being passed through flow in reactor is that 5～500ml/min carbon sources are reacted, and the response time is 0.5～1000min, in catalyst surface deposition or superscribe the carbon-coating of stratiform, obtains complex；
(2) complex of step (1) gained successively adds 0.01～2mol/L lead nitrate solution, 0.01～10mol/L sulfuric acid solution to react, products therefrom carries out filtering, cleaning, and i.e. obtains the carbon/lead sulfate composite of stratiform after drying at 60～250 DEG C；
Catalyst is more than one in potassium carbonate, sodium carbonate, and carbon source is more than one in methane, methanol, acetylene, ethanol, benzene, toluene, hexamethylene, acetonitrile, phthalocyanine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410773476.9A CN105895918A (en) | 2014-12-16 | 2014-12-16 | Negative electrode active material additive for lead storage battery |
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| CN201410773476.9A CN105895918A (en) | 2014-12-16 | 2014-12-16 | Negative electrode active material additive for lead storage battery |
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| CN201410773476.9A Pending CN105895918A (en) | 2014-12-16 | 2014-12-16 | Negative electrode active material additive for lead storage battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112072187A (en) * | 2020-10-12 | 2020-12-11 | 天能集团（河南）能源科技有限公司 | Lead-acid storage battery electrolyte and preparation method thereof |
| CN112133914A (en) * | 2020-04-09 | 2020-12-25 | 吉林省凯禹电化学储能技术发展有限公司 | Porous carbon-loaded ultra-small PbSO4Nano particle composite material, preparation thereof and application thereof in lead carbon battery anode |
| CN117352739A (en) * | 2023-11-09 | 2024-01-05 | 昆明理工大学 | Preparation method of additive capable of effectively inhibiting irreversible sulfation of negative electrode |
-
2014
- 2014-12-16 CN CN201410773476.9A patent/CN105895918A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112133914A (en) * | 2020-04-09 | 2020-12-25 | 吉林省凯禹电化学储能技术发展有限公司 | Porous carbon-loaded ultra-small PbSO4Nano particle composite material, preparation thereof and application thereof in lead carbon battery anode |
| CN112072187A (en) * | 2020-10-12 | 2020-12-11 | 天能集团（河南）能源科技有限公司 | Lead-acid storage battery electrolyte and preparation method thereof |
| CN112072187B (en) * | 2020-10-12 | 2021-11-19 | 天能集团（河南）能源科技有限公司 | Lead-acid storage battery electrolyte and preparation method thereof |
| CN117352739A (en) * | 2023-11-09 | 2024-01-05 | 昆明理工大学 | Preparation method of additive capable of effectively inhibiting irreversible sulfation of negative electrode |
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Application publication date: 20160824 |
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