CN101136487A - Lead acid battery containing nano carbon tube electrolyte - Google Patents
Lead acid battery containing nano carbon tube electrolyte Download PDFInfo
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- CN101136487A CN101136487A CNA200610111592XA CN200610111592A CN101136487A CN 101136487 A CN101136487 A CN 101136487A CN A200610111592X A CNA200610111592X A CN A200610111592XA CN 200610111592 A CN200610111592 A CN 200610111592A CN 101136487 A CN101136487 A CN 101136487A
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Abstract
This invention relates to a lead-acid battery with nm carbon tube electrolyte including a tank containing a space with a positive structure, a negative structure and electrolyte, in which, the electrolyte contains nm carbon tube material of preset weight percentage between 0.001-0.1 and the structures include positive and negative matrixes separately, and the positive matrix includes a positive reaction face coated with positive reaction material and the negative matrix includes a negative reaction face coated with negative reaction material for carrying out chemical reaction.
Description
Technical field
The invention relates to a kind of lead-acid battery, particularly about a kind of lead-acid battery that contains nano carbon tube electrolyte.
Background technology
Battery comprises chemical cell and physical battery two big classes, relevant with daily life is chemical cell, the battery that promptly is commonly called as, general general primary cell and the secondary cell (rechargeable battery) of being divided into of chemical cell, and more common secondary cell includes lead-acid battery (lead acid battery), nickel-cadmium cell (nickelcadmium battery), Ni-MH battery (nickel hydrogen battery), serondary lithium battery (secondary lithium battery), and lithium ion battery (lithium ion battery) and high-polymer lithium battery (polymer lithium battery) ... etc.
Still have at present the dependence of height on the market for the use of lead-acid battery, to use lead-acid battery all in a large number be its main power source for steam turbine car, UPS etc. such as.Characteristics of studying carefully its widely popular utilization are that it has that electromotive force is big, operating temperature is wide, simple in structure, technology maturation and advantage such as cheap, and it also has good cycle life, and economic benefit highly is provided.
In general lead-acid battery, all has battery cathode structure, battery cathode structure and electrolyte, and traditional electrolyte is to be modulated into dilution heat of sulfuric acid by sulfuric acid solution and water with a predetermined mix ratio, so that battery cathode structure, battery cathode structure and electrolyte carry out chemical reaction.Lead-acid battery formerly also has many relevant technology in the patented technology, for example announce No. 00293953 in the TaiWan, China patent of invention, it has disclosed and has a kind ofly improved the usefulness of utilizing lead accumulator by the carbon suspension liquid of the electrolytic oxidation gained of carbon anode in water system.
Known relevant improving technology for lead-acid battery is all the effective utilization that promotes lead-acid battery, so generally having the problem that manufacturing process is numerous and diverse or enhancing efficiency is limited exists, therefore, take a broad view of current correlation technique, still do not have simple and easy and the tangible improving technology of enhancing efficiency, to bring into play the best efficiency that lead-acid battery can provide.
Electrolyte adopts sulfuric acid solution in the lead-acid battery, is selecting sulfuric acid density 1.1g/ml to 1.6g/ml solution for use in the general electrolyte, and the percentage by weight that is scaled sulfuric acid is between 16 to 70 percentage by weights.Lead-acid battery can be divided into general non-colloid battery and colloid battery again, and colloid battery more can not ooze out sulfuric acid electrolyte, has the advantage of environmental protection.The difference of general non-colloid battery and colloid battery just is to contain in the electrolyte of colloid battery the above silicon dioxide of 3 percentage by weights of having an appointment, and the silicon dioxide of this concentration can form colloid in sulfuric acid solution, so be called colloid battery.Whether silicon dioxide can form colloid in sulfuric acid solution, except the percentage by weight of silicon dioxide, also depend on acid concentration and temperature in the sulfuric acid solution.
CNT (carbon nano-tube) is nano level tubulose material, it is one of the representative material of 21st century nanosecond science and technology, because this special structure, make it have very excellent and unique characteristics such as machinery, electronics, photoelectricity, heat conduction and chemistry, make it have many potential purposes, and extend to each different field in recent years fast.
In the battery association area, it is the electrode that is used in various batteries that CNT (carbon nano-tube) is used the most widely, and for example United States Patent (USP) 7,029,796,7,029,794,6,703,163,6,440,610 are used for CNT (carbon nano-tube) at the electrode of lithium battery with the TaiWan, China patent No. 1232607 and WO2005022666; United States Patent (USP) 6,706,431 CNT (carbon nano-tube) are used for the electrode of fuel cell; The TaiWan, China patent No. 1241029 is used for CNT (carbon nano-tube) at the electrode of solar cell; The TaiWan, China patent No. 1236779 is used for CNT (carbon nano-tube) at the electrode of Ni-MH battery; Chinese patent publication number CN1505186 and U.S. Patent Publication No. US2005181282 are used for CNT (carbon nano-tube) the both positive and negative polarity of lead-acid battery.United States Patent (USP) 6,917,181 disclose a kind of power supply unit, have wherein used the battery that has CNT (carbon nano-tube) on the electrode.United States Patent (USP) 6,805,985 also disclose a kind of act as a fuel hydrogen storage material of battery of CNT (carbon nano-tube) that uses.United States Patent (USP) 6,781,817 disclose the capacitor that has CNT (carbon nano-tube) on a kind of electrode.United States Patent (USP) 6,454,816 are used for the electrode of super capacitor with CNT (carbon nano-tube).
Use contains the electrolyte of CNT (carbon nano-tube) and the battery related application of enhanced performance, is the less field of being noted at present.Chinese patent publication number CN1505196 (authorizes publication number CN1237646C, patent No. ZL 02144682.2) a kind of lead acid accumulator that in electrolyte, contains nanometer carbon material of announcement, but this lead acid accumulator but the charging capacity of lead acid accumulator only improves 7.7% (bringing up to 4.2Ah by 3.9Ah), lifting is also not high enough, and the electrolyte of higher lifting effect still need be arranged on the industry.And this patented technology does not provide the effect of big electric current quick charge.
In addition, also there are some relevant patents state in the electrolyte of battery, to add the electrolyte carbon material that includes non-nano carbon pipe.Chinese patent publication number CN1697236 discloses the valve controlled sealed lead-acid accumulator that a kind of use contains nano-sized carbon electrolyte, wherein nano-carbon material is that the made diameter of electrolytic oxidation is the electrolytic oxidation carbon granule of 5-15nm, account for the 1-7% of electrolyte weight percentage, and not mentioned CNT (carbon nano-tube).The employed spherical carbon powder particle of this patent, differ widely with the rectangular and hollow tubular structure of CNT (carbon nano-tube), and CNT (carbon nano-tube) has splendid conductivity, adds special nanoscale tubular structure, can promote the rate travel of ion in electrolyte, promote the ionic conduction usefulness of lead-acid battery.Simultaneously, the concentration of nano-carbon material belongs to general known concentration range in this piece patent, promptly more than 1 percentage by weight, far above the CNT (carbon nano-tube) low concentration of being found among the present invention that good effect is arranged, promptly below 0.1 percentage by weight (1000ppm).In addition, all not mentioned battery of each piece patent more than for large current charge and discharge effect.More than the full text of each piece patent incorporate list of references at this.
Take a broad view of known lead-acid battery and be widely used in various fields, because of the mature technique of having attained for many years of its row makes people very be less than it technically to do improvement again.So also be widely used in daily life usual means such as steam turbine car and UPS,, certainly will provide higher economic benefit for its vast utilization if can improve its power supplying efficiency because of it.At the opportunity of global energy shortage, improve the service efficiency of electric supply installation, reduce expending of the energy, not less than being a contribution greatly.
Yet because the electrolyte in the traditional lead acid batteries forms the sulfuric acid concentration gradient easily, and the generation of sulfuric acid concentration gradient can make the sulfuric acid skewness in the electrolyte, and can reduce the speed that the electrolyte intermediate ion moves, therefore can directly influence every characteristic of electrolyte itself, for example, conductivity, thermal conductivity ... etc., the conductive effectiveness of lead-acid battery more can be influenced.
Summary of the invention
Purpose of the present invention is carried and being for a kind of lead-acid battery that contains nano carbon tube electrolyte, it utilizes a battery cathode structure, a battery cathode structure and an electrolyte that adds the CNT (carbon nano-tube) material to carry out chemical reaction, and makes this lead-acid battery have preferable conductive effectiveness.
For achieving the above object, the lead-acid battery that contains nano carbon tube electrolyte provided by the invention includes:
One battery cell body, enclosing structure has an accommodation space, and is equipped with the electrolyte of predetermined volumes in this accommodation space;
One battery cathode structure is arranged in this accommodation space, and this battery cathode structure comprises:
One positive terminal convexedly stretches in this battery cell body;
The anodal material main body of plural pieces is soaked the electrolyte of the accommodation space that places this battery cell body and is electrically connected on this positive terminal, and the anodal material main body of each sheet includes at least one anodal reaction surface, and is coated with anode reactant matter, to carry out chemical reaction;
One battery cathode structure is arranged in this accommodation space, and this battery cathode structure comprises:
One negative terminal convexedly stretches in this battery cell body;
Plural pieces base material of cathode body, soak the electrolyte of the accommodation space that places this battery cell body and isolate a preset distance and be electrically connected on this negative terminal with adjacent anodal material main body, each sheet base material of cathode body includes at least one negative reaction face, and be coated with the negative reaction material, to carry out chemical reaction;
One CNT (carbon nano-tube) material is added on a predetermined weight percent in the electrolyte of accommodation space of this battery cell body, and the predetermined weight percent of this CNT (carbon nano-tube) material is between 0.001 to 0.1 percentage by weight.
The described lead-acid battery that contains CNT (carbon nano-tube) wherein, includes silicon dioxide as adding material in this electrolyte, this silicon dioxide has a predetermined percentage by weight, and percentage by weight that should be predetermined is between 0.1 to 20 percentage by weight.
The described lead-acid battery that contains CNT (carbon nano-tube), wherein, the predetermined weight percent of this CNT (carbon nano-tube) material is between 0.003 to 0.072 percentage by weight.
The described lead-acid battery that contains CNT (carbon nano-tube), wherein the predetermined weight percent of this CNT (carbon nano-tube) material is between 0.005 to 0.018 percentage by weight.
The described lead-acid battery that contains CNT (carbon nano-tube), wherein, this CNT (carbon nano-tube) is selected from one of single-wall carbon tube, double-walled carbon pipe, many walls carbon pipe or its mixture.
The described lead-acid battery that contains CNT (carbon nano-tube), wherein, this many walls carbon external diameter of pipe is 2 to 100 nanometers, length is 0.1 to 80 micron.
The described lead-acid battery that contains CNT (carbon nano-tube), wherein, this single-wall carbon tube external diameter is 0.7 to 2 nanometer, length is 0.1 to 80 micron.
In other words, the present invention is for solving the technological means that problem adopted of known technology, be in a lead-acid battery, to include a battery cell body, a battery cathode structure and a battery cathode structure, wherein, this battery cell body encloses structure an accommodation space, and this battery cathode structure and this battery cathode structure are arranged in this accommodation space, more are equipped with the electrolyte of predetermined volumes in this accommodation space, are added with a predetermined weight percent in this electrolyte between 0.001 to 0.1 CNT (carbon nano-tube) material.
This battery cathode structure includes a positive terminal and the anodal material main body of plural pieces, wherein, this positive terminal convexedly stretches in this battery cell body, this positive pole material main body is soaked the electrolyte of the accommodation space that places this battery cell body, and be electrically connected on this positive terminal, the anodal material main body of each sheet all includes at least one anodal reaction surface, and is coated with anode reactant matter, to carry out chemical reaction.
This battery cathode structure includes a negative terminal and plural pieces base material of cathode body, wherein, this negative terminal convexedly stretches in this battery cell body, this base material of cathode body soaks the electrolyte of the accommodation space that places this battery cell body, and isolate a preset distance and be electrically connected on this negative terminal with adjacent anodal material main body, each sheet base material of cathode body includes at least one negative reaction face, and is coated with the negative reaction material, to carry out chemical reaction.
In the preferred embodiment of the present invention, add silica composition in the electrolyte in addition, with the equally distributed interpolation material of concentration that suspends and make sulfuric acid solution as aided nano carbon pipe.
The present invention contrasts the effect that known technology has:
Compared to known technology, the present invention is the CNT (carbon nano-tube) material that the electrolyte in this lead-acid battery is added with a predetermined weight percent, this CNT (carbon nano-tube) has splendid conductivity and has special nanoscale tubular structure, therefore can promote the rate travel of ion in electrolyte, so that this battery cathode structure and this negative battery structure are just, when the negative reaction material carries out chemical reaction preferable power supplying efficiency can be arranged, and this contains the formation that nano carbon tube electrolyte can suppress the sulfuric acid concentration gradient, and promote the speed that ion moves in electrolyte, to promote the ionic conduction usefulness of lead-acid battery itself, and higher economic benefit is provided, represent the splendid commercial surcharge of the present invention.
Simultaneously, add silica composition in the electrolyte of the present invention in addition.Because silicon dioxide has anti-sedimentation function, can be used as the interpolation material that aided nano carbon pipe suspends, except helping to prevent the CNT (carbon nano-tube) sedimentation, and also help the concentration of sulfuric acid solution evenly to distribute.
Compared to known technology, the present invention has following several innovation advantage:
(1) the present invention's lead-acid battery of containing nano carbon tube electrolyte can significantly promote capacitance, and the 0.1C discharge can improve 35%, and the 10C discharge can improve 51%, causes novel and the non-good character that can expect easily.This improvement in performance significantly surpasses the effect that other method is at present reached, and for example 7.7%.
(2) the present invention contains the lead-acid battery of nano carbon tube electrolyte, can effectively promote the useful life of battery, with regard to the shock-testing of 10C 40A heavy-current discharge and 1C 4A large current charge, use electrolyte of the present invention can extend to more than 500% than the period (life-span) of normal electrolyte.
(3) the present invention contains the lead-acid battery of nano carbon tube electrolyte, except significantly promote discharge capacity, the effect that also can promote the battery high current charge-discharge can quick charge, this also is another the main contribution and the advantage of electrolyte of the present invention.
(4) application of CNT (carbon nano-tube) is very extensive, be added on various materials in, comprise composite material, sports equipment, electronic product, its addition is generally all at the 1-10 percentage by weight.The present invention adopts extremely low CNT (carbon nano-tube) content, and the 0.001-0.1 percentage by weight is low concentration not seen before in the CNT (carbon nano-tube) application, and can reaches amazing good result.
(5) in the electrolyte of lead-acid battery of the present invention, CNT (carbon nano-tube) concentration is for being lower than 0.1 percentage by weight, promptly below the 1000ppm, far below adopting 1-7% weight ratio or even higher CNT (carbon nano-tube) concentration in the general correlation technique.Belong to the high price material based on CNT (carbon nano-tube), every g of value is between several dollars to tens of dollars.The present invention adopts the extremely low concentration CNT (carbon nano-tube) can reach good battery functi on to improve effect, possessed splendid low-cost advantage.
Specific embodiment of the present invention will be further described by following examples and accompanying drawing.
Description of drawings
Fig. 1 shows that the present invention contains the stereo appearance figure of the lead-acid battery of CNT (carbon nano-tube);
Fig. 2 shows that the present invention contains the three-dimensional exploded view of the lead-acid battery of CNT (carbon nano-tube).
Embodiment
1. material
The material that uses in the embodiment of the present invention is as follows:
The concentrated sulfuric acid-density is 1.84g/ml, and sulfuric acid concentration is the 95-98 percentage by weight;
CNT (carbon nano-tube) A-multiple-wall carbon nanotube, its external diameter are 10 to 40 nanometers, and length is 5 to 20 microns;
CNT (carbon nano-tube) B-multiple-wall carbon nanotube, its external diameter are 5 to 40 nanometers, and length is 0.1 to 3 micron;
CNT (carbon nano-tube) C-Single Walled Carbon Nanotube, its external diameter are 0.7 to 2 nanometer, and length is 0.5 to 30 micron;
Silicon-dioxide powdery-Aerosil 200 is available from Degussa company.
2. battery testing method,
Select for use the battery of the steam turbine car use of 12V 4Ah to test, this battery testing method has following two kinds:
A, the test of high rate low-rate discharge:
The test of high rate low-rate discharge is a discharge test that mixes, in this high rate low-rate discharge test, do 7 times discharge test altogether, wherein, be high rate 10C heavy-current discharge test (40A) for the first time with the 7th time discharge test, for the second time to the 6th time be low rate 0.1C low discharging current test (0.4A).And charging each time all is after being charged to 10.5V with 0.1C (0.4A) earlier, to use 1C (4A) to be charged to 200% of battery capacity again.
After the test of high rate low-rate discharge, can obtain three test results:
(1) 10C heavy-current discharge amount (primary test result);
(2) 0.1C low discharging current amount;
(3) high rate discharge capacity loss late.
Wherein this high rate discharge capacity loss late is with after the first time, the high rate discharge capacity subtracted for the second time the high rate discharge capacity, with its result divided by the first time high rate discharge capacity can calculate.
High rate discharge capacity loss late is the mode in a kind of simulated battery life-span, when high rate discharge capacity loss late less than 50% the time, expression simulated battery life test have by, yet, the simulated battery life test has by representing that promptly the normal battery life test will pass through, so the calculating of high rate discharge capacity loss late is a kind of simulated battery life test of shortening the time.If when for the first time high rate is lower than 1 minute discharge time, represent that promptly this battery can't the high rate discharge.
B, shock-testing:
With high rate 10C 40A heavy-current discharge and 1C 4A large current charge is a circulation, and it is with 0.1C 0.4A low current charge that normal battery is used charging, with 40A discharge time be termination less than 1 minute, and its period of retest.Because of charging is that 1C charges normal 10 times of 0.1C,, represent that promptly this battery life is preferable, and when period reached a predetermined value, this battery can be as quick charging battery if measured period is many more.
3. electrolyte is made
Electrolyte adopts sulfuric acid solution in the lead-acid battery, is selecting sulfuric acid density 1.1g/ml to 1.6g/ml solution for use in the general electrolyte, and the percentage by weight that is scaled sulfuric acid is between 16 to 70 percentage by weights.
Use the concentrated sulfuric acid solution (wherein sulfuric acid concentration be 98 percentage by weights) of density as 1.84g/ml, add in the pure water of capacity, preparation becomes the sulfuric acid solution that density is 1.33g/ml (wherein sulfuric acid concentration is 43 percentage by weights), and this sulfuric acid solution i.e. 1 electrolyte as a comparative example.
Embodiment 1-26
Get the sulfuric acid solution that above-mentioned density is 1.33g/ml,, add CNT (carbon nano-tube) and silicon-dioxide powdery respectively, fully stirred 24 hours, mix, be mixed with the electrolyte of embodiment 1 to 26 through using mixer according to listed prescription in the table 1.Each electrolyte is added in the test battery, at this battery variety 12V 4Ah that adopts the steam turbine car to use.Test result is showed in the table 1.
The performance of electrolyte in non-colloid battery of various CNT (carbon nano-tube) of table 1. and silica concentration
| Numbering | The CNT (carbon nano-tube) weight ratio | The CNT (carbon nano-tube) kind | The silica weight ratio | 0.4A discharge, hour | The 40A discharge, second | Shock-testing (period) | Agree life |
| Comparative example 1 | There is not CNT (carbon nano-tube) in the electrolyte | Do not have | Do not have | 10 | 150 | 30 | Qualified |
| Embodiment 1 | 0.0005％ | A | 1％ | 10 | 150 | 43 | |
| Embodiment | |||||||
| 2 | 0.001％ | A | Do not have | 10.5 | 155 | 52 | |
| Embodiment | |||||||
| 3 | 0.001％ | A | 1％ | 10.5 | 158 | 76 | |
| Embodiment | |||||||
| 4 | 0.003％ | A | 1％ | 10.5 | 170 | 124 | |
| Embodiment | |||||||
| 5 | 0.003％ | B | 1％ | 10.5 | 174 | 131 | Qualified |
| Embodiment 6 | 0.003％ | C | 1％ | 11 | 180 | 146 | Qualified |
| Embodiment 7 | 0.005％ | A | 1％ | 11.5 | 189 | >150 | Qualified |
| Embodiment 8 | 0.007％ | A | Do not have | 12 | 168 | 118 | Qualified |
| Embodiment 9 | 0.007％ | A | 0.1％ | 12 | 180 | 130 | |
| Embodiment | |||||||
| 10 | 0.007％ | A | 0.5％ | 12 | 188 | 135 | Qualified |
| Embodiment 11 | 0.007％ | A | 1％ | 12.5 | 195 | 142 | Qualified |
| Embodiment 12 | 0.007 | A | 3％ | 12.5 | 202 | >150 | Qualified | |
| Embodiment 13 | 0.007％ | B | 1％ | 12.5 | 206 | >150 | Qualified | |
| Embodiment 14 | 0.007％ | C | 1％ | 13.5 | 226 | >150 | Qualified | |
| Embodiment 15 | 0.009％ | A | 1％ | 12 | 195 | >150 | Qualified | |
| Embodiment 16 | 0.009％ | B | 1％ | 12 | 201 | >150 | Qualified | |
| Embodiment 17 | 0.009％ | C | 1％ | 13 | 219 | >150 | Qualified | |
| Embodiment 18 | 0.018％ | A | 1％ | 11.5 | 185 | >150 | Qualified | |
| Embodiment 19 | 0.036％ | A | 1％ | 11 | 175 | >150 | Qualified | |
| Embodiment 20 | 0.036％ | B | 1％ | 11 | 179 | >150 | | |
| Embodiment | ||||||||
| 21 | 0.072％ | A | Do not have | 10.5 | 148 | 112 | | |
| Embodiment | ||||||||
| 22 | 0.072％ | A | 1％ | 11 | 170 | 135 | Qualified | |
| Embodiment 23 | 0.1％ | A | Do not have | 10 | 112 | 47 | Qualified | |
| Embodiment 24 | 0.1％ | A | 1％ | 10.5 | 155 | 68 | Qualified | |
| Embodiment 25 | 0.2％ | A | 1％ | 10 | 85 | -- | Defective * | |
| Embodiment 26 | 0.5％ | A | 1％ | 9.5 | 25 | -- | Defective * |
* on both positive and negative polarity, all find to have tangible CNT (carbon nano-tube) depositional phenomenon;
Many walls of CNT (carbon nano-tube) A-carbon pipe, external diameter 10 to 40 nanometers, 5 to 20 microns of length;
Many walls of CNT (carbon nano-tube) B-carbon pipe, external diameter 5 to 40 nanometers, 0.1 to 3 micron of length;
CNT (carbon nano-tube) C-single-wall carbon tube, external diameter 0.7 to 2 nanometer, 0.5 to 30 micron of length.
As can be known, CNT (carbon nano-tube) content between 0.1 percentage by weight (being 1000ppm), all has favorable effects at 0.001 percentage by weight (being 10ppm) in above-mentioned test.The proportion (being 30-720ppm) between 0.003% weight ratio to 0.072% weight ratio that CNT (carbon nano-tube) is preferable, the proportion of CNT (carbon nano-tube) the best is (being 50-180ppm) between 0.005% weight ratio to 0.018% weight ratio.Simultaneously, can find out by embodiment 8 to 12 and the result of embodiment 21 to 24, in the dilution via adding silicon dioxide, the usefulness that can promote nano carbon tube electrolyte.
Compared to the battery that adds comparative example 1 electrolyte, add the battery that the present invention contains the electrolyte of CNT (carbon nano-tube) and promote 35% (the 0.4A discharge rose to 13.5 hours by 10 hours) in that the 0.1C discharge capacity is the highest, the 10C discharge capacity promotes 51% (rising to 226 seconds in 150 seconds) approximately.And but the big width of cloth of the period that is obtained by shock-testing rises to more than 500%, and this contains the battery of nano carbon tube electrolyte as can be known, and its life-span will significantly prolong by general battery, and the aspect also has the advantage of using big electric current quick charge in addition.
In addition, in above-mentioned CNT (carbon nano-tube) content range, use different types of CNT (carbon nano-tube), all can obtain good effect.And with CNT (carbon nano-tube) C, i.e. the best results of Single Walled Carbon Nanotube.
By the test result of above battery as can be known, when the low concentration of CNT (carbon nano-tube) below 0.001 percentage by weight, can't fill part its effect of performance; And when CNT (carbon nano-tube) concentration when 0.1 percentage by weight is above, can begin assemble to form agglomerate because of too intensive through observing CNT (carbon nano-tube), these agglomerates can hinder moving of electrolyte intermediate ion on the contrary, thereby the effect of reduction battery.
See also shown in Figure 1ly, it shows that the present invention contains the stereo appearance figure of the lead-acid battery of CNT (carbon nano-tube), and Fig. 2 shows that the present invention contains the three-dimensional exploded view of the lead-acid battery of CNT (carbon nano-tube).As shown in the figure, this lead-acid battery 100 comprises a battery cell body 1, a battery cathode structure 2 and a negative battery structure 3.Wherein, this battery cell body 1 encloses structure an accommodation space 10, and this battery cathode structure 2 is arranged in this accommodation space 10 with this negative battery structure 3, and is equipped with the electrolyte 4 of predetermined volumes in this accommodation space.
This battery cathode structure 2 includes a positive terminal 21 and the anodal material main body 22 of plural pieces, wherein, this positive terminal 21 convexedly stretches in this battery cell body 1, this positive pole material main body 22 is soaked the electrolyte 4 of 10 of accommodation spaces that place this battery cell body 1, and be electrically connected on this positive terminal 21, and the anodal material main body 22 of each sheet includes at least one anodal reaction surface 221.
On this positive pole reaction surface 221, be coated with anode reactant matter 222, to carry out chemical reaction, wherein, this anode reactant matter 222 has the CNT (carbon nano-tube) material of a predetermined weight percent, and the CNT (carbon nano-tube) material of this predetermined weight percent is to change its percentage by weight according to the application of this lead-acid battery 100.
This battery cathode structure 3 includes a negative terminal 31 and plural pieces base material of cathode body 32, wherein, this negative terminal 31 convexedly stretches in this battery cell body 1, this base material of cathode body 32 soaks the electrolyte 4 of 10 of accommodation spaces that place this battery cell body 1, and isolate preset distances and be electrically connected on this negative terminal 31 with adjacent anodal material main body 22, and each sheet base material of cathode body 32 includes at least one negative reaction face 321, on this negative reaction face 321, be coated with negative reaction material 322, to carry out chemical reaction.
Be added with CNT (carbon nano-tube) material 5 in this electrolyte 4 between 0.001 to 0.1 percentage by weight, and this CNT (carbon nano-tube) material 5 is many walls carbon pipe or single-wall carbon tube, this many walls carbon external diameter of pipe is 5 to 40 nanometers, and length is 0.1 to 20 micron; This single-wall carbon tube external diameter is 0.7 to 2 nanometer, and length is 0.5 to 30 micron.
In the present invention, this positive pole material main body 22 can be made by lead-containing alloy with base material of cathode body 32.This electrolyte 4 is sulfuric acid solution, so this battery cell body 1 need have good acid resistance, in addition, this battery cell body 1 also need have high mechanical properties, anti-vibration, shock resistance, with the characteristic of high-low temperature resistant, to keep the complete of these lead-acid battery 100 structures.And the composition of this anode reactant matter 222 and negative reaction material 322 is mainly brown lead oxide.
When practical application, also include silicon dioxide in the electrolyte 4 of this interpolation CNT (carbon nano-tube) material 5 and add material as one, wherein, this silicon dioxide can promote the suspension of CNT (carbon nano-tube) in electrolyte.And this silicon dioxide has a predetermined percentage by weight, and percentage by weight that should be predetermined is between 1 to 20 percentage by weight.
This lead-acid battery 100 is when practical application, key reaction is all carried out on this battery cathode structure 2 and this battery cathode structure 3, when this lead-acid battery 100 carried out exoelectrical reaction, the anode reactant matter 222 that this battery cathode structure 2 utilizes its anodal reaction surface 22 to adhere to was carried out reduction reaction (PbO
2+ 3H
++ HSO
4 -+ 2e
-→ PbSO
4+ 2H
2O), electronics flows into this battery cathode structure 2 by this positive terminal 21, and reacts with brown lead oxide, hydrogen ion and hydrogen sulfate ion, generates lead sulfate and water.
The negative reaction material 322 that this battery cathode structure 3 utilizes its negative reaction face 32 to adhere to carries out oxidation reaction (Pb (s)+HSO
4 -→ PbSO
4+ H
++ 2e
-), consuming lead and hydrogen sulfate ion and generate lead sulfate, electronics and hydrogen ion, this electronics flows out via negative terminal 31, constitutes a discharge path.
Can find out by above-mentioned chemical reaction, the exoelectrical reaction meeting continues to consume brown lead oxide, the lead of this battery cathode structure 3 and the sulfuric acid of this electrolyte 4 of this battery cathode structure 2, when sulfuric acid content is crossed the reaction of should charging when hanging down with activation the two poles of the earth, make sulfuric acid concentration reply the action that to discharge again.
During the charging reaction, this battery cathode structure 2 carries out oxidation reaction (PbSO
4+ 2H
2O → PbO
2+ 3H
++ HSO
4 -+ 2e
-), decompositing brown lead oxide, hydrogen ion and hydrogen sulfate ion, this battery cathode structure 3 is then carried out reduction reaction (PbSO
4+ H
++ 2e
-→ Pb (s)+HSO
4 -), generate lead and hydrogen sulfate ion.Therefore, the brown lead oxide, lead and the sulfuric acid that consume in the time of can producing exoelectrical reaction during the charging reaction are replied sulfuric acid concentration gradually, can carry out exoelectrical reaction more to external world.
Via the foregoing description as can be known, the present invention sees through the CNT (carbon nano-tube) material 5 of interpolation predetermined weight percent in the electrolyte 4 of lead-acid battery 100, can improve electrical efficiency, the discharge capacity of this lead-acid battery 100, and prolong the useful life of this lead-acid battery 100.
CNT (carbon nano-tube) material 5 used in the present invention, because of it has excellent electric conductivity and has special nanoscale tubular structure, can promote the rate travel of ion in electrolyte, when making the positive and negative electrode reactive material of this battery cathode structure and this negative battery structure carry out chemical reaction preferable power supplying efficiency can be arranged, and this contains the formation that nano carbon tube electrolyte can suppress the sulfuric acid concentration gradient, to promote the ionic conduction usefulness of lead-acid battery itself.The interpolation CNT (carbon nano-tube) material 5 of proper proportion has improved the conductive capability of this electrolyte 4 with this anode reactant matter 222 greatly, has also improved the reaction speed of this anode reactant matter 222.
Above embodiment explanation only is preferred embodiment explanation of the present invention, and all those skilled in the art are when doing other all improvement and variation according to the above embodiment of the present invention explanation.Yet all improvement and variation that these are done according to the embodiment of the invention are in the claim that still belongs to invention spirit of the present invention and define.
Claims (7)
1. lead-acid battery that contains nano carbon tube electrolyte includes:
One battery cell body, enclosing structure has an accommodation space, and is equipped with the electrolyte of predetermined volumes in this accommodation space;
One battery cathode structure is arranged in this accommodation space, and this battery cathode structure comprises:
One positive terminal convexedly stretches in this battery cell body;
The anodal material main body of plural pieces is soaked the electrolyte of the accommodation space that places this battery cell body and is electrically connected on this positive terminal, and the anodal material main body of each sheet includes at least one anodal reaction surface, and is coated with anode reactant matter, to carry out chemical reaction;
One battery cathode structure is arranged in this accommodation space, and this battery cathode structure comprises:
One negative terminal convexedly stretches in this battery cell body;
Plural pieces base material of cathode body, soak the electrolyte of the accommodation space that places this battery cell body and isolate a preset distance and be electrically connected on this negative terminal with adjacent anodal material main body, each sheet base material of cathode body includes at least one negative reaction face, and be coated with the negative reaction material, to carry out chemical reaction;
One CNT (carbon nano-tube) material is added on a predetermined weight percent in the electrolyte of accommodation space of this battery cell body, and the predetermined weight percent of this CNT (carbon nano-tube) material is between 0.001 to 0.1 percentage by weight.
2. the lead-acid battery that contains CNT (carbon nano-tube) as claimed in claim 1, wherein, include silicon dioxide in this electrolyte as adding material, this silicon dioxide has a predetermined percentage by weight, and percentage by weight that should be predetermined is between 0.1 to 20 percentage by weight.
3. the lead-acid battery that contains CNT (carbon nano-tube) as claimed in claim 1, wherein, the predetermined weight percent of this CNT (carbon nano-tube) material is between 0.003 to 0.072 percentage by weight.
4. the lead-acid battery that contains CNT (carbon nano-tube) as claimed in claim 1, wherein the predetermined weight percent of this CNT (carbon nano-tube) material is between 0.005 to 0.018 percentage by weight.
5. the lead-acid battery that contains CNT (carbon nano-tube) as claimed in claim 1, wherein, this CNT (carbon nano-tube) is selected from one of single-wall carbon tube, double-walled carbon pipe, many walls carbon pipe or its mixture.
6. the lead-acid battery that contains CNT (carbon nano-tube) as claimed in claim 5, wherein, this many walls carbon external diameter of pipe is 2 to 100 nanometers, length is 0.1 to 80 micron.
7. the lead-acid battery that contains CNT (carbon nano-tube) as claimed in claim 5, wherein, this single-wall carbon tube external diameter is 0.7 to 2 nanometer, length is 0.1 to 80 micron.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610111592XA CN101136487A (en) | 2006-08-28 | 2006-08-28 | Lead acid battery containing nano carbon tube electrolyte |
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|---|---|---|---|
| CNA200610111592XA CN101136487A (en) | 2006-08-28 | 2006-08-28 | Lead acid battery containing nano carbon tube electrolyte |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493498A (en) * | 2018-04-20 | 2018-09-04 | 北京君禾科技有限公司 | Lead accumulator production method and lead accumulator, method for producing electrolyte and electrolyte |
| CN110299569A (en) * | 2019-08-09 | 2019-10-01 | 常熟市万隆电源技术研发有限公司 | A kind of large capacity nano-colloid battery |
-
2006
- 2006-08-28 CN CNA200610111592XA patent/CN101136487A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493498A (en) * | 2018-04-20 | 2018-09-04 | 北京君禾科技有限公司 | Lead accumulator production method and lead accumulator, method for producing electrolyte and electrolyte |
| CN108493498B (en) * | 2018-04-20 | 2020-04-03 | 北京君禾科技有限公司 | Lead storage battery production method, lead storage battery, electrolyte production method and electrolyte |
| CN110299569A (en) * | 2019-08-09 | 2019-10-01 | 常熟市万隆电源技术研发有限公司 | A kind of large capacity nano-colloid battery |
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