CN101136488A - Electrolyte additive agent containing nano carbon tube - Google Patents
Electrolyte additive agent containing nano carbon tube Download PDFInfo
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- CN101136488A CN101136488A CNA2006101117821A CN200610111782A CN101136488A CN 101136488 A CN101136488 A CN 101136488A CN A2006101117821 A CNA2006101117821 A CN A2006101117821A CN 200610111782 A CN200610111782 A CN 200610111782A CN 101136488 A CN101136488 A CN 101136488A
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Abstract
This invention relates to an additive containing carbon nm tubes including water, carbon nm tubes of preset weight percentage between 0.1-30 and SiO2 0.1-40 taking weight percentage of water 100% as the basis, in which, the nm carbon tubes and the SiO2 are mixed in water uniformly to form an additive with nm carbon tubes, which can be diluted and added into the electrolyte of lead-acid batteries and sulfate in a preset concentration is added as an additive material during the process.
Description
Technical field
The invention relates to a kind of electrolyte that is used for lead-acid battery, particularly about a kind of electrolyte that contains CNT (carbon nano-tube) and silicon dioxide.
Background technology
Look into battery and mostly be made up of yin, yang electrode, electrolyte and shell, wherein, negative electrode is in order to the acquisition superior performance, and anode is to carry out reacted surface in order to increase to amass, and electrolyte generally also is called electrolyte.
After redox reaction has taken place in the anode and cathode of electrolyte in battery, electronics produces electric current by the outside line transmission, at internally charged ion then is to transmit between anode and cathode by electrolyte, therefore adopts a good electrolyte can make the discharge of anode and cathode more efficient.And in the selection of electrolyte material, must have not active material with electrode react, have high-k, low-viscosity with improve ionic conductance, have higher boiling point, low melting point is with the operating temperature range of augmentation battery and the characteristics such as stable in properties of itself.
And the internal resistance of battery is decided by the impedance of the resistance and the ion flow of battery lead plate, and in the charge and discharge process, the impedance of battery lead plate is constant, and still, the impedance of ion flow will change to some extent with the increase and decrease of the variation of concentration of electrolyte and charged ion.
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 system 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, and the kind and the characteristic of the silicon dioxide that uses.
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).
The related application of CNT (carbon nano-tube) in battery electrolyte is the present less field of being noted.Chinese patent publication number CN1505191 (authorizes publication number CN 1219336C, patent No. ZL02144681.4) announcement is a kind of is suitable for adding in the lead-acid accumulator electrolyte, include the aqueous additive of nanometer carbon material and dispersant, wherein nanometer carbon material is 100 with the ratio of dispersant: 10-100: 60.Learn that through conversion the 1-dimention nano carbonaceous material accounts for the 0.63-45.5% of electrolyte weight ratio in this additive.This additive is added in the lead acid accumulator, can improve the active material utilization of lead acid accumulator, but only make the charging capacity of lead acid accumulator improve 7.7% (bringing up to 4.2Ah) by 3.9Ah.But in this patent,, the electrolyte of higher lifting effect need be arranged still on the industry to the lifting of the charging capacity of battery and not high enough.And this patented technology does not provide the effect of big electric current quick charge.
In addition, use the carbon material of non-nano carbon pipe to add in the electrolyte of battery, some relevant patents are also arranged.For example to disclose a kind of carbon powder particle be the following lead acid accumulator carbon activator of 15nm to Chinese patent publication number CN1440087, and wherein carbon powder particle is by the electrolytic oxidation manufactured.Purity greater than 99.5% graphitic carbon plate, is adopted DC power supply, the dry powder particle after the carbon activator liquid of the made 5-15nm of electrolytic oxidation and the oven dry.This carbon activator is added in the brand-new lead-acid battery, can use the discharge capacity of storage battery to increase by 19% (being increased to 100 minutes) by 84 minutes.But the employed material of this case is spherical carbon powder particle, differs widely with the rectangular and hollow tubular structure of CNT (carbon nano-tube).And the diameter of the structure of this spherical carbon dust is 5-15nm, and CNT (carbon nano-tube) is of a size of diameter 0.5-100nm, length 0.3-50 μ m, and CNT (carbon nano-tube) has splendid conductivity and special nanoscale tubular structure, can promote the rate travel of ion in electrolyte.In addition, though this patent is mentioned the effect that large current charge and discharge can be provided in summary, there is no any data can have this effect really for this activator of evidence.Chinese patent publication number CN1697236 discloses a kind of electrolyte that has nano-sized carbon that is used in valve controlled sealed lead-acid accumulator, interior phosphoric acid and nano-carbon material, wherein phosphoric acid accounts for electrolyte 0.5-0.9 percentage by weight, and nano-carbon material accounts for the 1-7% of electrolyte weight percentage; This electrolyte can increase the discharge capacity and the useful life of battery, but this case and not mentioned CNT (carbon nano-tube).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).More than the full text of each piece patent incorporate list of references at this.
Its composition material of the electrolyte of conventional batteries and the concentration of itself all can influence the usefulness of battery itself, and the as easy as rolling off a log formation sulfuric acid concentration of traditional electrolyte gradient, 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 the conductivity of electrolyte itself, more can influence the conductive effectiveness of battery.
Because the dispersing and mixing of CNT (carbon nano-tube) need long period (20-30 hour) mix, in the consideration of practical application, should adopt higher concentration that CNT (carbon nano-tube) and silicon dioxide are hybridly prepared into the additive that fine dispersion suspends earlier, dilution and add sulfuric acid and make and reach effective low concentration nano carbon tube electrolyte and use again before the use, so can bring into play to save mixing the time, and reduce the economic interests that volume is transported in the nano carbon tube electrolyte storage.
Summary of the invention
Purpose of the present invention is carried and being for a kind of concentrated additive that contains CNT (carbon nano-tube) that is added in the lead-acid battery, this concentrated additive is in being added into lead-acid battery the time, through dilution, became the suitable electrolyte that uses of selected lead-acid battery earlier so that should concentrate electrolyte.
Another object of the present invention is to provide a kind of and contain CNT (carbon nano-tube) and silicon dioxide is hybridly prepared into the electrolysis additive that fine dispersion suspends, this electrolysis additive can be added in the electrolyte of lead-acid battery.
Another object of the present invention is to provide a kind of electrolysis additive that CNT (carbon nano-tube) and silicon dioxide are hybridly prepared into that contains, this electrolysis additive can be added in the electrolyte of lead-acid battery through dilution.
For achieving the above object, the present invention mixes the CNT (carbon nano-tube) and the silicon dioxide of predetermined percentage by weight with water, and what this CNT (carbon nano-tube) and silicon dioxide were hybridly prepared into the fine dispersion suspension contains the CNT (carbon nano-tube) additive.This additive can become electrolysis additive behind easy thin up process to a predetermined concentration when using, can be for being filled in the electrolyte of lead-acid battery.
In the preferred embodiment of the present invention, this electrolysis additive is in being added into this lead-acid battery the time, and the sulfuric acid that also can optionally be added with predetermined concentration reaches effective low concentration nano carbon tube electrolyte and uses as adding material, making.
In detail, the electrolysis additive that contains CNT (carbon nano-tube) provided by the invention includes:
One water;
One CNT (carbon nano-tube), this CNT (carbon nano-tube) have a predetermined percentage by weight, and this predetermined percentage by weight is between 0.1 to 30 percentage by weight, and this percentage by weight is that the weight with water is 100% to calculate;
A kind of silicon dioxide, it has a predetermined percentage by weight, and this predetermined percentage by weight is between 0.1 to 40 percentage by weight, and this percentage by weight is that the weight with water is 100% to calculate; This CNT (carbon nano-tube) and silicon dioxide evenly are mixed in this water, and form an additive that contains CNT (carbon nano-tube), and this electrolysis additive can be through being added in the electrolyte of lead-acid battery after the dilution.
The described electrolysis additive that contains CNT (carbon nano-tube), wherein, this electrolysis additive is in being added into this lead-acid battery the time, and the sulfuric acid that also is added with predetermined concentration forms the electrolyte of this lead-acid battery as adding material.
The described electrolysis additive 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 electrolysis additive 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 electrolysis additive 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.
The described electrolysis additive that contains CNT (carbon nano-tube), wherein, this dilution comprises adding sulfuric acid, and this electrolyte is met the following conditions:
(1) make and satisfy sulfuric acid in the electrolyte after this dilution concentration is between 16 to 70 percentage by weights in the aqueous solution, this percentage by weight is that the total weight with sulfuric acid in the electrolyte after the dilution and water is 100% calculating;
(2) percentage by weight that makes CNT (carbon nano-tube) in the electrolyte after this dilution is between 0.001 to 0.1 percentage by weight, and this percentage by weight is that the total weight with sulfuric acid in the electrolyte after the dilution and water is 100% calculating;
This electrolyte can be filled in the lead-acid battery electrolyte as this lead-acid battery.
The described electrolysis additive that contains CNT (carbon nano-tube), wherein, also comprise interpolation silicon dioxide in this dilution, make in the electrolyte after this dilution dioxide-containing silica between 0.1 to 20 percentage by weight, this percentage by weight is that the total weight with sulfuric acid in the electrolyte after the dilution and water is 100% calculating.
The present invention contrasts the effect that known technology has:
Compared to known technology, the present invention is hybridly prepared into water, CNT (carbon nano-tube) and silicon dioxide and contains the CNT (carbon nano-tube) additive, but and this CNT (carbon nano-tube) stable dispersion be suspended in this additive.This additive can become electrolysis additive behind easy thin up process to a predetermined concentration when using, can be for being filled in the electrolyte of lead-acid battery.So can bring into play to save mixing the time, and reduce the economic interests that volume is transported in the nano carbon tube electrolyte storage.
Owing to contain CNT (carbon nano-tube), have splendid conductivity and have the characteristic of special nanoscale tubular structure in the electrolyte, therefore can promote the rate travel of ion in electrolyte, and promote the reaction rate of battery by this CNT (carbon nano-tube).
Moreover the CNT (carbon nano-tube) in the electrolyte of the present invention can be impelled that the concentration of sulfuric acid solution evenly distributes in the electrolyte by capillarity, and solves the shortcoming of the sulfuric acid concentration gradient that traditional electrolyte all can form, thereby promotes the usefulness of electrolyte and battery.Simultaneously, the silica composition in the electrolysis additive of the present invention has anti-sedimentation function, can be used as the interpolation material that aided nano carbon pipe suspends, and except helping to prevent the CNT (carbon nano-tube) sedimentation, and also helps the concentration of sulfuric acid solution evenly to distribute.
Compared to known technology, the present invention has following several innovation advantage:
(1) for lead-acid battery, the present invention contains the electrolysis additive of CNT (carbon nano-tube), can significantly promote capacitance after being diluted to predetermined concentration, and the 0.1C discharge can improve 35%, the 10C discharge can improve 63%, 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% or 19%.
(2) the present invention contains the electrolysis additive of CNT (carbon nano-tube), can be after being diluted to predetermined concentration, can effectively promote the useful life of battery, with regard to the shock-testing of big electric current 40A discharge of 10C and the big electric current 4A charging of 1C, 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 electrolysis additive of CNT (carbon nano-tube), can be after being diluted to predetermined concentration, except significantly promote discharge capacity, the effect that more 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) CNT (carbon nano-tube) belongs to hydrophobic material, is difficult in dispersion suspension in the aqueous solution.At present existing many researchs focus on uses different dispersants to promote the dispersion and the suspension of CNT (carbon nano-tube), comprises various interfacial agents and organic and inorganic salts.The present invention is based on the extremely low CNT (carbon nano-tube) concentration of employing, be engaged in the hyperbaric sulfuric acid solution (1.1-1.6g/ml), can effectively promote the suspension of CNT (carbon nano-tube) and the effect that performance promotes the electrolyte function, must not use any dispersant fully.Aspect in addition, the present invention also uses the auxiliary suspending agent of silicon dioxide as CNT (carbon nano-tube), and promotes the suspension of CNT (carbon nano-tube) in electrolyte.This uses silicon dioxide aided nano carbon pipe to suspend and the method for different any dispersants also is an innovative technology in the present invention.
(5) application of CNT (carbon nano-tube) is very extensive, has been added in the various materials, comprises composite material, sports equipment, electronic product, and its addition is generally all at the 1-10 percentage by weight.The present invention contains the electrolysis additive of CNT (carbon nano-tube), can after being diluted to predetermined concentration, adopt extremely low CNT (carbon nano-tube) content, 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.
(6) the present invention contains the electrolysis additive of CNT (carbon nano-tube), can be after being diluted to predetermined concentration, 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 lead-acid battery function to improve effect, possessed splendid low-cost advantage.
(7) because the dispersing and mixing of CNT (carbon nano-tube) need the long period mix, in the consideration of economic benefit, the present invention adopts high concentration to mix (20-40 hour) for a long time, and the CNT (carbon nano-tube) fine dispersion is suspended, and becomes the concentrate of the electrolysis additive that contains CNT (carbon nano-tube).Can simple and easyly promptly reach effective low concentration nano carbon tube electrolyte use during use with making in this additive dilution and the adding electrolyte.So can bring into play to save mixing the time, and reduce the economic interests that volume is transported in the nano carbon tube electrolyte storage.For example from the CNT (carbon nano-tube) concentrated additive of 0.7% and 7% weight ratio, the dilution preparation becomes the nano carbon tube electrolyte of 0.007% weight ratio, its dilution ratio reach respectively 100 times with 1000 times, have and significantly reduce the economic interests that mix dispersion for a long time.
Embodiment
Specific embodiment of the present invention will be further described by following examples and accompanying drawing.
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-
200, 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, be low rate 0.1C low discharging current test (0.4A) to the 6th time for the second time with the 7th time discharge test.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:
Be charged as a circulation with the big electric current 40A of high rate 10C discharge with the big electric current 4A of 1C, 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.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 battery 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, and the kind and the characteristic of the silicon dioxide that uses.Electrolyte of the present invention is applicable to general non-colloid battery and colloid battery.
A. preparation contains the electrolysis additive of CNT (carbon nano-tube)
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 1-23
Get the 100g pure water, with pure water heavily is 100% calculating, each adds the CNT (carbon nano-tube) (promptly adding 5g and 15g respectively) of 5 percentage by weights and 15 percentage by weights, and respectively add 34 percentage by weight silicon-dioxide powderies (being 34g), respectively through using mixer fully to stir 24 hours, mix, be mixed with the additive J (CNT (carbon nano-tube) accounts for 5 percentage by weights) and additive K (CNT (carbon nano-tube) accounts for 15 percentage by weights) that contain CNT (carbon nano-tube) and silicon dioxide respectively.
According to listed prescription in the table 1, in electrolysis additive J and K, add sulfuric acid and thin up to predetermined CNT (carbon nano-tube) concentration, regulating and making sulfuric acid solution density is 1.33g/ml, and adds an amount of silicon-dioxide powdery, mixes a little, electrolyte promptly completes.
Be mixed with the electrolyte of embodiment 1 to 23 according to said method.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 various CNT (carbon nano-tube) additives of table 1. are through the performance of dilution as non-electrolyte of colloidal cell
| Numbering | The CNT (carbon nano-tube) weight ratio, % | The CNT (carbon nano-tube) kind | Adopt additive types | 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 | Do not have | 10 | 150 | 30 | Defective |
| Embodiment 1 | 0.0005 | A | J | 0.003 | 10 | 150 | 34 | Qualified |
| Embodiment 2 | 0.001 | A | J | 0.007 | 10.5 | 156 | 64 | Qualified |
| Embodiment 3 | 0.001 | A | J | 1 | 10.5 | 159 | 66 | Qualified |
| Embodiment 4 | 0.003 | A | K | 1 | 10.5 | 179 | 125 | Qualified |
| Embodiment 5 | 0.005 | A | J | 1 | 11.5 | 185 | >150 | Qualified |
| Embodiment 6 | 0.007 | A | J | 0.05 | 12 | 164 | 124 | Qualified |
| Embodiment 7 | 0.007 | A | J | 0.1 | 12 | 170 | 130 | Qualified |
| Embodiment 8 | 0.007 | A | J | 0.5 | 12 | 182 | 132 | Qualified |
| Embodiment 9 | 0.007 | A | J | 1 | 12.5 | 184 | 135 | Qualified |
| Embodiment 10 | 0.007 | A | J | 3 | 12.5 | 194 | >150 | Qualified |
| Embodiment 11 | 0.007 | A | K | 1 | 12.5 | 208 | >150 | Qualified |
| Embodiment 12 | 0.007 | B | J | 1 | 12.5 | 212 | >150 | Qualified |
| Embodiment 13 | 0.007 | C | J | 1 | 13.5 | 244 | >150 | Qualified |
| Embodiment 14 | 0.009 | A | J | 1 | 12 | 198 | >150 | Qualified |
| Embodiment 15 | 0.009 | B | J | 1 | 12 | 202 | >150 | Qualified |
| Embodiment 16 | 0.009 | C | K | 1 | 13 | 228 | >150 | Qualified |
| Embodiment 17 | 0.018 | A | J | 1 | 11.5 | 192 | >150 | Qualified |
| Embodiment 18 | 0.036 | A | J | 1 | 11 | 184 | >150 | Qualified |
| Embodiment 19 | 0.036 | A | K | 1 | 11 | 180 | >150 | Qualified |
| Embodiment 20 | 0.072 | A | J | 1 | 11 | 182 | 144 | Qualified |
| Embodiment 21 | 0.1 | A | K | 0.3 | 10.5 | 150 | 64 | Qualified |
| Embodiment 22 | 0.1 | A | K | 1 | 10.5 | 162 | 80 | Qualified |
| Embodiment 23 | 0.5 | A | J | 1 | 9.5 | 22 | -- | Defective * |
* on both positive and negative polarity, all find to have tangible many walls of CNT (carbon nano-tube) depositional phenomenon 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.
By the test result of above battery as can be known, when using the present invention to contain CNT (carbon nano-tube) and silicon dioxide electrolysis additive, forming electrolyte through simple dilution and after adding sulfuric acid, wherein 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).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 6 to 10 and the result of embodiment 21 to 22, in the dilution via the content of control 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 63% (rising to 244 seconds in 150 seconds) approximately.And but the big width of cloth of the period that is obtained by shock-testing rises to 500% more than (30 times rise to more than 150 times), this contains the battery of nano carbon tube electrolyte as can be known, 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 the CNT (carbon nano-tube) behind the dilution back 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.
B. the colloidal electrolyte prescription is made and test
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).
Get the sulfuric acid solution that above-mentioned density is 1.33g/ml, add in addition the silicon dioxide with 6 percentage by weights, this percentage by weight is to be 100% to calculate with sulfuric acid solution weight, through fully stirring, mix, leave standstill and make this electrolyte formation gel, promptly be mixed with the colloidal electrolyte that contains comparative example 2.
Embodiment 24-44
Get aforesaid additive J and the electrolysis additive K that contains CNT (carbon nano-tube) and silicon dioxide.According to listed prescription in the table 2, in electrolysis additive J and electrolysis additive K, add sulfuric acid and thin up to predetermined CNT (carbon nano-tube) concentration, and making sulfuric acid solution density is 1.33g/ml, and add an amount of silicon-dioxide powdery, mix a little, leave standstill and make this electrolyte formation gel, i.e. colloidal electrolyte is finished in preparation.
Be mixed with the colloidal electrolyte of embodiment 24 to 44 according to said method.Each colloidal 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 2.
The various CNT (carbon nano-tube) additives of table 2. are through the performance of dilution as electrolyte of colloidal cell
| Numbering | The CNT (carbon nano-tube) weight ratio, % | The CNT (carbon nano-tube) kind | Adopt additive types | 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 | Do not have | 10 | 150 | 30 | Qualified |
| Comparative example 2 | There is not CNT (carbon nano-tube) in the colloidal electrolyte | Do not have | Do not have | 6 | 11 | --* | --* | --* |
| Embodiment 24 | 0.0005 | A | J | 6 | 11 | 174 | 10 | Defective |
| Embodiment 25 | 0.001 | A | J | 6 | 11 | 143 | 56 | Qualified |
| Embodiment 26 | 0.002 | A | J | 6 | 11.5 | 166 | 120 | Qualified |
| Embodiment 27 | 0.002 | A | K | 6 | 11.5 | 162 | 114 | Qualified |
| Embodiment 28 | 0.005 | A | J | 6 | 11.5 | 176 | >150 | Qualified |
| Embodiment 29 | 0.005 | A | K | 6 | 11.5 | 184 | >150 | Qualified |
| Embodiment 30 | 0.007 | A | J | 6 | 12 | 197 | >150 | Qualified |
| Embodiment 31 | 0.007 | A | J | 9 | 12 | 186 | >150 | Qualified |
| Embodiment 32 | 0.007 | A | J | 12 | 12 | 172 | >150 | Qualified |
| Embodiment 33 | 0.007 | A | K | 6 | 12 | 194 | >150 | Qualified |
| Embodiment 34 | 0.007 | B | J | 6 | 12.5 | 202 | >150 | Qualified |
| Embodiment 35 | 0.007 | C | J | 6 | 13.5 | 218 | >150 | Qualified |
| Embodiment 36 | 0.009 | A | J | 6 | 12.5 | 198 | >150 | Qualified |
| Embodiment 37 | 0.009 | B | J | 6 | 13 | 206 | >150 | Qualified |
| Embodiment 38 | 0.009 | C | K | 6 | 14 | 230 | >150 | Qualified |
| Embodiment 39 | 0.018 | A | J | 6 | 12 | 190 | >150 | Qualified |
| Embodiment 40 | 0.036 | A | J | 6 | 11.5 | 178 | >150 | Qualified |
| Embodiment 40 | 0.036 | A | K | 6 | 11.5 | 182 | >150 | Qualified |
| Embodiment 41 | 0.072 | A | J | 6 | 11 | 176 | >150 | Qualified |
| Embodiment 42 | 0.1 | A | J | 6 | 11 | 160 | 75 | Qualified |
| Embodiment 43 | 0.2 | A | J | 6 | 10.5 | 88 | 40 | Defective * * |
| Embodiment 44 | 0.5 | A | K | 6 | 10 | 40 | -- | Defective * * |
* the present generally the highest 3-4C current discharge that only reaches of colloid battery does not still have 10C heavy-current discharge function.
* all finds to have tangible CNT (carbon nano-tube) depositional phenomenon on both positive and negative polarity
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.
By the test result of above battery as can be known, when using the present invention to contain CNT (carbon nano-tube) and silicon dioxide electrolysis additive, forming electrolyte through simple dilution and after adding sulfuric acid, wherein 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).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.
Compared to the colloid battery that adds comparative example 2 electrolyte, add the colloid battery that the present invention contains the electrolysis additive of CNT (carbon nano-tube) and promote 27% (the 0.4A discharge rose to 14 hours by 11 hours) in that the 0.1C discharge capacity is the highest.10C discharge capacity and shock-testing aspect be not because the present generally the highest 3-4C current discharge that only reaches of colloid battery still has 10C (40A) heavy-current discharge function, so can only compare with the non-colloid battery (comparative example 1) that uses general electrolyte.Experimental result shows, adding the present invention contains the colloid battery of the electrolysis additive of CNT (carbon nano-tube), can promote the 10C discharge capacity and reach 53% (rising to 230 seconds in 150 seconds), but the period of shock-testing greatly then the width of cloth rise to 500% more than (30 times rise to) more than 150 times.This contains the colloid 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 the CNT (carbon nano-tube) behind the dilution back 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.
By above-mentioned every embodiment of the invention as can be known, the present invention contains the electrolysis additive of CNT (carbon nano-tube), the electrolyte that contains CNT (carbon nano-tube) that can be through being diluted to predetermined concentration and be applicable to general non-colloid lead-acid battery and colloid lead-acid battery, and significantly improve every effect.
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. electrolysis additive that contains CNT (carbon nano-tube) includes:
One water;
One CNT (carbon nano-tube), this CNT (carbon nano-tube) have a predetermined percentage by weight, and this predetermined percentage by weight is between 0.1 to 30 percentage by weight, and this percentage by weight is that the weight with water is 100% to calculate;
A kind of silicon dioxide, it has a predetermined percentage by weight, and this predetermined percentage by weight is between 0.1 to 40 percentage by weight, and this percentage by weight is that the weight with water is 100% to calculate; This CNT (carbon nano-tube) and silicon dioxide evenly are mixed in this water, and form an additive that contains CNT (carbon nano-tube), and this electrolysis additive can be through being added in the electrolyte of lead-acid battery after the dilution.
2. the electrolysis additive that contains CNT (carbon nano-tube) as claimed in claim 1, wherein, this electrolysis additive is in being added into this lead-acid battery the time, and the sulfuric acid that also is added with predetermined concentration forms the electrolyte of this lead-acid battery as adding material.
3. the electrolysis additive 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.
4. the electrolysis additive that contains CNT (carbon nano-tube) as claimed in claim 3, wherein, this many walls carbon external diameter of pipe is 2 to 100 nanometers, length is 0.1 to 80 micron.
5. the electrolysis additive that contains CNT (carbon nano-tube) as claimed in claim 3, wherein, this single-wall carbon tube external diameter is 0.7 to 2 nanometer, length is 0.1 to 80 micron.
6. the electrolysis additive that contains CNT (carbon nano-tube) as claimed in claim 1, wherein, this dilution comprises adding sulfuric acid, and this electrolyte is met the following conditions:
(1) make and satisfy sulfuric acid in the electrolyte after this dilution concentration is between 16 to 70 percentage by weights in the aqueous solution, this percentage by weight is that the total weight with sulfuric acid in the electrolyte after the dilution and water is 100% calculating;
(2) percentage by weight that makes CNT (carbon nano-tube) in the electrolyte after this dilution is between 0.001 to 0.1 percentage by weight, and this percentage by weight is that the total weight with sulfuric acid in the electrolyte after the dilution and water is 100% calculating;
This electrolyte can be filled in the lead-acid battery electrolyte as this lead-acid battery.
7. the electrolysis additive that contains CNT (carbon nano-tube) as claimed in claim 6, wherein, also comprise interpolation silicon dioxide in this dilution, make in the electrolyte after this dilution dioxide-containing silica between 0.1 to 20 percentage by weight, this percentage by weight is that the total weight with sulfuric acid in the electrolyte after the dilution and water is 100% calculating.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104051796A (en) * | 2014-05-29 | 2014-09-17 | 天能电池(芜湖)有限公司 | Formulation and preparation method of storage battery colloid mother liquor |
| CN107154519A (en) * | 2017-06-06 | 2017-09-12 | 明光市裕阳农业有限公司 | A kind of battery liquid additive and preparation method thereof |
| CN107403964A (en) * | 2017-07-26 | 2017-11-28 | 合肥尚强电气科技有限公司 | A kind of electrolyte additive for lead-acid accumulator and preparation method thereof |
-
2006
- 2006-08-28 CN CNB2006101117821A patent/CN100559646C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104051796A (en) * | 2014-05-29 | 2014-09-17 | 天能电池(芜湖)有限公司 | Formulation and preparation method of storage battery colloid mother liquor |
| CN107154519A (en) * | 2017-06-06 | 2017-09-12 | 明光市裕阳农业有限公司 | A kind of battery liquid additive and preparation method thereof |
| CN107403964A (en) * | 2017-07-26 | 2017-11-28 | 合肥尚强电气科技有限公司 | A kind of electrolyte additive for lead-acid accumulator and preparation method thereof |
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