CN103415492A - Porous carbon product and use thereof - Google Patents

Porous carbon product and use thereof Download PDF

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CN103415492A
CN103415492A CN2011800687901A CN201180068790A CN103415492A CN 103415492 A CN103415492 A CN 103415492A CN 2011800687901 A CN2011800687901 A CN 2011800687901A CN 201180068790 A CN201180068790 A CN 201180068790A CN 103415492 A CN103415492 A CN 103415492A
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precursor substance
particle
template
carbon
template particles
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CN103415492B (en
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C.诺伊曼
J.贝克
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Heraeus Quarzglas GmbH and Co KG
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
    • C04B38/0032—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors one of the precursor materials being a monolithic element having approximately the same dimensions as the final article, e.g. a paper sheet which after carbonisation will react with silicon to form a porous silicon carbide porous body
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract

A known method for producing a porous carbon body comprises providing a template of inorganic template material which comprises interconnected pores, providing a precursor substance for carbon, infiltrating the pores of the template with the precursor substance, carbonizing the precursor substance and removing the template with formation of the porous carbon product. Starting therefrom, to provide a method which allows a cost-effective production of a porous carbon structure also with thick wall thicknesses, it is suggested according to the invention that precursor substance particles of fusible material and template particles are provided and a powder mixture is formed from the particles, and that the powder mixture is heated before or during carbonization according to method step (d) in such a manner that precursor substance melt penetrates into the pores of the template particles.

Description

Porous carbon product and uses thereof
Specification sheets
The present invention relates to the method for the preparation of the porous carbon product, the method comprises the following steps:
(a) provide the template formed by the inorganic mould material that comprises the hole be interconnected,
(b) provide the precursor substance of carbon,
(c) with this precursor substance, permeate the hole of described template,
(d) this precursor substance of carbonization,
(e) remove this template, to form the porous carbon product.
In addition, the present invention relates to the suitable purposes of this carbon products.
The material all in one piece molding of carbon is for example for the electrode of fuel cell, super capacitor and store battery (secondary cell), and as the solid support material of storage medium, chromatographic applications or the catalytic process of the sorbent material of liquid and gas, gas and as the material of machinery or pharmaceutical engineering.
Prior art
The application of the electrode of rechargeable lithium battary needs under low loss of charge, reversibly to embed and the electrode materials of removal lithium embedded.Simultaneously, purpose is the high charge capacity of short as far as possible duration of charging and battery.Therefore, expectation maximum pore rate (rate of permeation), the while is also expected the electrode materials on as far as possible little surface.Electrode materials with large surface represents quite high loss of charge, and this shows that it is essentially irreversible loss during the embedding for the first time of lithium.
DE 29 46 688 A1 disclose the method for preparing porous carbon by the interim preform (so-called template) that adopts porous material.In this literary composition, the precursor substance of carbon is deposited on to surface and is at least 1m 2In the hole of the template of the inorganic mould material of/g.SiO 2Gel, sintered glass, aluminum oxide or other porous heat-resistant oxide compound are regarded as the suitable mould material of described template.The porosity of described mould material is at least 40%, and mean pore size is the scope of 3nm to 2 μ m.
Recommend the polymerizable organic materials, for example the mixture of phenol and hexamine or resol resin are the precursor substance of carbon.This mixture is with liquid or with also polymerization in the hole of gas introducing template.After polymerization and carbonization subsequently, remove the inorganic mould material of this template, for example, by being dissolved in NaOH or hydrofluoric acid.
Produced like this particulate state or laminar carbon products, this product has roughly the vesicular structure corresponding to the distribution of material of template, and its bases fit is as the parent material of preparation Li battery electrode.
For high and fast charging ability, it is conclusive easily entering internal surface.Under this background, so-called " classifying porous property " result is favourable.Large surface can provide by the hole of nanometer range.For improving the accesibility in these holes, the delivery system by continuous macropore is connected them ideally.
In US 2005/0169829 A1, narrated the material all in one piece carbon products of the hierarchical porous structure with such macropore and mesopore.In order to prepare hierarchical porous structure, prepared such SiO 2Template, by diameter, be wherein that the silicon-dioxide bead of 800nm to 10 μ m and dispersion that polymerizable material forms heat in mould, thereby polymerization produces porous silica, and it is dry and polymerization fully after removing excess liq.
Then, with the precursor substance of carbon, flood the SiO obtained by this way 2The hole of template, become carbon by this carbon precursor substance carbonization, and by being dissolved in HF or NaOH, remove this SiO subsequently 2Template.Thus obtained carbon products also shows the pore structure of the distribution of material that roughly meets described template.Be dissolved in the phenol resins of tetrahydrofuran (THF) (THF) as precursor substance.
Technical purpose
But the common graphitized carbon precursor material for infiltration can not dissolve with higher concentration, and contains a certain amount of soluble component.For example, the solubleness of mesophase pitch in THF is less than 10 volume %, so that, after the solvent evaporation, keep not filling more than 90% initial pore volume of filling.Carbonization at the remaining coating volume of carbon precursor material by subsequently further reduces, but not obvious.
On the contrary, the carbon precursor of the carbohydrate form of replacement is sugar for example, demonstrates high-dissolvability, but after the solvent evaporation, remaining sugar loses approximately 50% initial mass in carbonization process, so that keep macropore volume not fill herein.
Therefore, the infiltration with carbonization subsequently produces the deposition carbon-coating of only little thickness usually.For reaching the porous carbon structure of technical useful wall thickness, therefore usually must carry out repeatedly such infiltration and carbonization process by succeedingly.But such plural process has improved manufacturing cost and they may cause ununiformity, for example, due to the obstruction gradually of permeating channel.
The purpose of this invention is to provide and can low-cost prepare porous carbon structure and it has the method for thick wall thickness.
In addition, the objective of the invention is the suitable purposes according to carbon products of the present invention.
Describe, in general terms of the present invention
For described method, this purpose initial by the method for the above-mentioned type realizes according to the present invention, precursor substance particle and the template particles of fusible material wherein are provided, and powdered mixture is made by described particle, and according to method steps (d) thus carbonization before or during heat in one way described powdered mixture and make during the precursor substance melt infiltrates the hole of described template particles.
In the method according to the invention, the precursor substance of carbon is heating when contacting with described template, and softening or fusing in this process, thereby it can infiltrate in the hole of template.The solvent that can ignore the carbon precursor substance.
Yet even have been found that in the situation that the mould material wettability is good, if this template exists with material all in one piece, this " directly infiltration " with template of liquefaction precursor substance will not produce the success of expectation yet.In the situation that without extraordinary precaution, operator will obtain for irregular occupying in the too little depth of penetration of melting precursor substance and hole.For head it off, according to the present invention, provide in advance the powder prepared from described foraminous die plate material and described precursor substance, described powder evenly mixes each other, and the uniform powder mixture is heated to the degree that the particle of precursor substance will melt.
This melt can directly infiltrate adjacent template particles.Described uniform powder mixture guarantee the melting precursor substance always with the template particles close contact, thereby in the whole pore volume of mould material to be infiltrated, realize being uniformly distributed and occupying.The high temperature kept between the melting period of precursor substance helps the better wettability of described template surface, thereby, even in the situation that single permeates, has also realized the high compactedness of pore volume.
The infiltration in the carbonization of precursor substance and the hole of template particles is carried out simultaneously, or carries out subsequently.Because the use of solvent is rejected, so the contraction of precursor substance is only due to the decomposition between the carbon period and evaporative process.In this respect, shrink grading only depends on the carbon content of precursor substance.
Inorganic mould material is only as machinery and thermally-stabilised skeleton for deposition and calcination carbon precursor substance.For example, after removing (passing through chemical dissolution), the gained carbon products is substantially free of mould material.
Template particles is more in small, broken bits, and under all the other identical process conditions, infiltration will be sooner, more effective and more even.Template particles is for example by grinding from the porous insert of mould material or by pulverizing the layer from mould material, by suppressing from the powder of mould material or making by sol-gel method or shotting.The little desirable monodispersed size-grade distribution for example realized by screening is favourable for the method according to this invention.
The powder of precursor substance also can be by grinding or pulverizing or obtain by the atomization melt.
After two kinds of powder had been mixed with each other evenly, the heating powder mixture was to the degree of precursor substance melting, and infiltrated in the hole of template powder in strong wetting mode.Herein, can be simultaneously or carbonization precursor substance subsequently.
After carbonization, obtain the matter piece (mass) that wherein carbonization precursor substance and mould material closely mix each other.By the described matter piece of etch, remove mould material, thereby will keep the carbon skeleton of the precursor substance of carbonization.
When providing template particles to comprise the soot deposits method, result is particularly advantageous, by hydrolysis or pyrolysis, starting material are changed into to the mould material particle in the method, and described particle deposition is on deposition surface, to form the cigarette ash body from mould material, and the cigarette ash body is broken into template particles.
In this variant according to the inventive method, form template and comprise the soot deposits method.In this method, liquid or gas initial substance generation chemical reaction (hydrolysis or pyrolysis), and by vapour deposition, be solid ingredient on deposition surface.Reaction zone is for example burner flame or electric arc (plasma body).By means of this class plasma body or CVD sedimentation, it is for example known with title OVD, VAD, MCVD, PCVD or FCVD method, with technical scale, prepared by synthetic silica glass, stannic oxide, titanium nitride and other synthetic materials.
Herein, it is important that mould material is present on deposition surface for the qualified deposition mould material for the preparation of template, and this deposition surface can be for example container, plug, flat board or strainer.Guaranteed that like this it is low keeping the temperature of deposition surface, thereby prevented the mould material deposited dense sintering.Obtained as the thermofixation thus of intermediate product but " the cigarette ash body " of porous.
With the preparation method by " sol-gel approach ", compare, the soot deposits method is cheap method, and the method can prepare template at low cost with technical scale.
For the cigarette ash body obtained by this way, result is that it is advantageous particularly, and it has the anisotropic mass distribution of hierarchical porous structure because the preparation method shows.Reason is at reaction zone, and vapour deposition produces the primary particle of the mould material of granularity in nanometer range, this particle with its mode agglomeration to deposition surface and exist or be gathered on deposition surface with the form of similar spherical agglomerate; These will also be called as " second particle " hereinafter.In primary particle and in second particle, namely between primary particle, having chamber and hole in especially little nanometer range is so-called mesopore, and forms larger chamber or hole between each second particle.
By pulverizing or grinding the template particles obtained, also show the hierarchy with few peak pore size distribution be predefined in mould material thus.
In the soot deposits method, mould material also can be with the form preparation of cigarette ash powder, and it further is processed into template particles subsequently in shotting, pressing, slurry process or sintering process.Particle or thin slice should be called as intermediates.
The layer of template material of making by soot deposits can, with little reactive force fragmentation, obtain the template particles with thin layer or laminar form.
This category feature is that the template particles of non-spherical morphology is particularly conducive to and is used in according in the inventive method.
Reason is the particle with spherical morphology, and namely the particle of spherical shape or approximate circle spherical-like morphology, have little surface for its volume.By contrast, the particle of non-spherical morphology shows the more S/V of vast scale, and this becomes easily the infiltration of precursor substance and be even.
In this respect, sheet or bar-shaped structure are than being at least 5, and preferably at least 10 template particles result is particularly advantageous.
Herein " structure ratio " is interpreted as the max architecture width of particle and the ratio of its thickness.Therefore, at least 5 structure is than the max architecture width that means particle than its thickness large 5 times at least.This class particle is essentially sheet or bar-shaped form, and is characterised in that the large surface of two substantially parallel extensions, and the infiltration by this melt surface precursor substance can occur relatively rapidly, because the thickness less of volume to be filled.
The thickness of template particles is less, the infiltration of melting precursor substance more simply, more even.In this respect, when the average thickness range of template particles is 10 μ m to 500 μ m, the scope of 20 μ m to 100 μ m preferably, while particularly preferably being less than 50 μ m, result is favourable.
The template particles that thickness is less than 10 μ m has little physical strength, and aggravation forms obvious hierarchical porous structure.Under the thickness that is greater than 500 μ m, more and more be difficult to guarantee the uniformly penetrating of melting precursor substance.
When the precursor material grains is made spherical and mean particle size and is less than 50 μ m and preferably is less than 20 μ m, be conducive to the even mixing from the particle of mould material and precursor material.
Due to the spherical moulding of particle, improved and the mixing of aspherical particle from mould material.When the particle from precursor substance is slightly less than the particle of precursor substance, also supported above-mentioned saying.Yet, the granularity that is less than 1 μ m tend to dust formation and and not preferred.
By the ratio of mixture of precursor substance and mould material, set the compactedness in hole.Preferably, precursor substance particle and template particles are with the volume ratio of 0.05 to 1.6 scope, and preferably the volume ratio with 0.1 to 0.8 scope mixes.
Under 0.05 ratio of mixture, only with the little thickness of one deck, cover the internal surface of mould material, thereby obtain just spongy carbon net.Therefore, even less ratio of mixture not preferred.By contrast, under 1.6 ratio of mixture, depend on the initial apertures volume of mould material, operator obtain the pore structure of substantially filling up.
Preferably, mould material is SiO 2.
Cost that can be relatively low, on technical scale, by means of the soot deposits method, used the synthetic SiO of cheap starting raw material preparation 2.During calcining, SiO 2High temperature resistant.By starting SiO 2With carbon generates SiC, react the preset temperature upper limit (being about 1000 ℃).According to method steps (e), remove synthetic SiO by chemical dissolution 2The mould material of form.
Pitch preferably is suitable as the carbon precursor substance.
Pitch, particularly " mesophase pitch " are the carbonaceous materials of the regular liquid crystal structure of tool.After carbonization, infiltrate through the graphite sample deposition that pitch in the carbon structure hole causes carbon, it forms the shell of core/shell mixture, thereby and the micropore of closed carbon structure, and do not stop up the chamber between stacking layer.
Perhaps, carbohydrate is as the carbon precursor substance.
Carbohydrate, especially sugar, for example sucrose, fructose or glucose, be agraphitic carbon precursor substance.
Preferably, carbon products is pulverized to (divided) and become porous particle carbon in small, broken bits.
In the method according to the invention, carbon products obtains with material all in one piece or with thin layer or laminar form usually, and can easily be ground into less particle.Due to the structure of template, the particle obtained after pulverizing has hierarchical porous structure, and for example by standard paste or slurry process, further is processed into molding or layer.
About the purposes of carbon products, above-mentioned purpose obtains according to the present invention, and wherein porous carbon product according to the present invention is for the preparation of the electrode of rechargeable type lithium cell.
The electrode of rechargeable type lithium cell comprises that two by the carbon-coating of the single-material electrode of making and the combined electrode be made of a variety of materials.
Preferred embodiment
The present invention now explains in more detail with reference to embodiment and accompanying drawing.Be specially
Fig. 1 illustrates for the preparation of SiO with schematic diagram 2The device of cigarette ash body,
Fig. 2 illustrates the SEM image of the first embodiment of the porous carbon product according to the inventive method acquisition with hierarchical porous structure,
Fig. 3 illustrates the SEM image of the second embodiment of the porous carbon product according to the inventive method acquisition with hierarchical porous structure, and
Fig. 4 is illustrated in the thermogravimetric analysis figure during the template that in oxygen-containing atmosphere, heated asphalt permeates.
Device shown in Fig. 1 is for the preparation of SiO 2The cigarette ash body.A plurality of flame hydrolysis burners 2 that are arranged in a row are set to the support tube 1 along aluminum oxide.Flame hydrolysis burner 2 is arranged on common burner block 3, burner block 3 is parallel and to-and-fro movement between two turning points static with respect to longitudinal axes 4 with the longitudinal axes 4 with support tube 1, and removable on its vertical direction, as shown in direction arrow 5 and 6.Burner 2 consists of silica glass; Their spacings each other are 15cm.
Flame hydrolysis burner 2 is provided with burner flame 7 separately, and its main propagation direction is vertical with the longitudinal axes 4 of support tube 1.By means of flame hydrolysis burner 2, SiO 2Particle deposition is on the cylinder jacket surface of the support tube 1 around its longitudinal axis 4 rotations, thus porous SiO 2Blank 8 successively is accumulated as external diameter 400mm.Each SiO 2The mean thickness of soot layer is about 50 μ m.
Use respectively oxygen and hydrogen as burner gas to 2 chargings of flame hydrolysis burner and SiCl 4As forming SiO 2The raw material of particle.This is in the amplitude to-and-fro movement of two burner spacings (being 30cm) burner block 3.During deposition process, the medial temperature on stock surface 9 is set to about 1200 ℃.
After deposition process finished, acquisition length was 3m, and external diameter is 400mm, and internal diameter is the porous SiO of 50mm 2The pipe of cigarette ash (Smoker's ash tube).Temperature during the cigarette ash body forms keeps relatively low, thus SiO 2The cigarette ash material has low relative mean density, is 22% (based on the density 2.21g/cm of silica glass 3).
Preposition experiment
(1) in first test, under nitrogen, in vessel in heating to 300 ℃, the pitch that obtains thickness is bathed by mesophase pitch.By SiO 2The material all in one piece sample of cigarette ash body immerses in the pitch bath, and again shifts out after 30 minutes.Found that, molten asphalt only infiltrates the thickness that is less than 1mm in the cigarette ash body.
The temperature of (2) then, pitch being bathed is increased to 400 ℃.Mesophase pitch is still thickness at this temperature.The unrealized obvious increase of penetration degree in the cigarette ash body.At the temperature of about 500 ℃, pitch starts coking significantly evaporation.
The first embodiment
Grind cigarette ash body sample.Because the cigarette ash body is successively accumulated, the layer that one deck is positioned at another layer top demonstrates the ablation tendency under high mechanical force exists, thereby obtains non-spherical, thin layer or laminar particle, and its thickness range is 20 μ m to 50 μ m.For the purpose of further processing, by screening, separating the length of side is 500 μ m to 1, the granularity part of 000 μ m.Max architecture width (mean value) is about 20 with the ratio of mean thickness.
By grinding mesophase pitch and preparing by screening the asphalt powder that the basic spheroidal particle that is 5 μ m to 20 μ m by granularity forms.
Asphalt powder and cigarette ash body particle evenly mix each other with the volume ratio of 1.6:1, and this granular mixture is heated to the temperature of 300 ℃.The pitch of thickness is by little SiO 2Cigarette ash body particle surrounds and infiltrates in hole.Thereby select the volume ratio pitch of pitch and cigarette ash body particle to fill described hole, thereby no longer include significantly idle pore volume and almost completely consume at this.
After permeating 30 minutes, temperature is brought up to 700 ℃, thereby make asphalt carbonization.The compound matter piece of porous is by occupying outside and inner (being the inwall in described hole) non-spherical porous SiO 2Particle forms, and it has graphitisable carbon-coating.
Remove subsequently SiO 2Cigarette ash body particle, wherein introduce compound matter piece in hydrofluoric acid (fluoric acid) bath.At SiO 2Particle after etching off, obtains the porous carbon basic products with following structure, and this structure represents initial SiO basically 2The inverse replica of cigarette ash body particle (negative copy) (hereinafter also being called " phase antitemplate ").The phase antitemplate be characterized as hierarchical porous structure, wherein a large amount of relatively large hole paths (macropore) extend through the surface tissue of other minute cracks.
By phase antitemplate purification, drying and fragmentation, thereby it splits into the carbon thin slice.According to the SEM image of Fig. 2, thus obtained the have intrinsic hole of a large amount of different sizes and the carbon structure in chamber are shown.The chamber of large-size extends through the minute crack surface of channel mode.According to the BET method, measure than internal surface area the about 25m obtained 2The observed value of/g.
The second embodiment
As described as reference embodiment 1, preparation SiO 2Cigarette ash body particle and mesophase pitch particle.Volume ratio with 0.4:1 is evenly mixed asphalt powder and cigarette ash body particle each other, this granular mixture is heated to the temperature of 300 ℃.The pitch of thickness is by little SiO 2Cigarette ash body particle surrounds and infiltrates in described hole.Selected the ratio of pitch and cigarette ash body particle, thereby pitch can not be filled described hole fully.
After reference embodiment 1 explains infiltration and carbonization, obtain the compound matter piece of porous, wherein non-spherical porous SiO 2Cigarette ash body particle occupies outside and partial interior, and it has graphitisable carbon-coating.Subsequently, by etch in hydrofluoric acid, remove SiO 2Cigarette ash body particle, obtain the basic products of porous carbon, and its structure is derived from initial cigarette ash body particle, and it is configured to have the fine-structure mesh of thin-walled, yet wherein a large amount of relatively large hole paths extend through the surface tissue of other minute cracks.
Carbon products easily splits into the carbon thin slice.According to the SEM image of Fig. 3, its structure is shown.The intrinsic hole of a large amount of different sizes and chamber extend through the minute crack surface in the mode of passage.According to the BET method, measure than internal surface area, obtain about 50m 2The observed value of/g.
Before Fig. 4 is illustrated in carbonization, according to embodiment 1, process the result (according to DIN 51005 and DIN 51006) of the thermogravimetric analysis in bitumen-impregnated cigarette ash body particle matter piece sample process.This sample heats in pure argon, and measures loss in weight in this.To be plotted on the y axle in the loss in weight Δ G based on initial weight %, and will in ℃ treatment temp T be plotted on the x axle.
Therefore, from the temperature of about 300 ℃, observe weight drop for the first time, it can be classified as the burning at activated carbon center and follow-up carbonization.Until temperature is about 600 ℃, weight descends 4.4%, then with saturated end, corresponding to the weight of pure carbon-coating.
The carbon thin slice obtained according to the inventive method consists of the porous carbon with hierarchy.They are suitable for preparing the electrode layer of rechargeable type lithium cell, especially combined electrode particularly well.

Claims (12)

1. for the preparation of the method for porous carbon product, the method comprises the following steps:
(a) provide the template of the inorganic mould material that comprises the hole be interconnected,
(b) provide the precursor substance of carbon,
(c) with the hole of this precursor substance infiltrating formwork,
(d) this precursor substance of carbonization,
(e) remove this template, to form the porous carbon product,
It is characterized in that, precursor substance particle and the template particles of fusible material are provided, and powdered mixture is formed by described particle, feature also be before the carbonization according to method steps (d) or during, heat in one way described powdered mixture, thereby the precursor substance melt is infiltrated in the hole of described template particles.
2. method according to claim 1, it is characterized in that, provide template particles to comprise the soot deposits method, wherein by hydrolysis or pyrolysis, make starting material change into the mould material particle, and make described particle deposition on deposition surface, to form the cigarette ash body from mould material, and this cigarette ash body is broken into to template particles.
3. method according to claim 1 and 2, is characterized in that, described template particles has aspheric form.
4. method according to claim 3, is characterized in that, described template particles is sheet or bar-shaped, and its structure, than being at least 5, is preferably at least 10.
5. according to the described method of aforementioned arbitrary claim, it is characterized in that, the mean thickness of described template particles, in the scope of 10 μ m to 500 μ m, preferably, in the scope of 20 μ m to 100 μ m, particularly preferably is less than 50 μ m.
6. according to the described method of aforementioned arbitrary claim, it is characterized in that, described precursor substance particle is made spherical, and mean particle size preferably is less than 20 μ m for being less than 50 μ m.
7. according to the described method of aforementioned arbitrary claim, it is characterized in that, described precursor substance particle and template particles are with the volume ratio of 0.05 to 1.6 scope, and preferably the volume ratio with 0.1 to 0.8 scope mixes mutually.
8. according to the described method of aforementioned arbitrary claim, it is characterized in that, described mould material is SiO 2.
9. according to the described method of aforementioned arbitrary claim, it is characterized in that, pitch is used as to the carbon precursor substance.
10. according to the described method of aforementioned arbitrary claim, it is characterized in that, carbohydrate is used as to the carbon precursor substance.
11. according to the described method of aforementioned arbitrary claim, it is characterized in that, carbon products be ground into to porous particle carbon in small, broken bits.
12. described porous carbon product is for the preparation of the purposes of the electrode of rechargeable type lithium cell.
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