Patent Grant
10109847
This application is a 35 U.S.C. § 371 National Stage Application of PCT/CN2012/085898, filed on Dec. 5, 2012, the disclosure of which is incorporated herein by reference in its entirety.
The present invention relates to a sulfur-carbon composite material, its application in lithium-sulfur battery and a method for preparing said composite material.
With mobile electrical devices being more and more popular in our daily life, their power supply has inevitably become one important concern. Currently, lithium secondary batteries are being widely adopted, while high demands with regard to the electrical and mechanical properties thereof shall be satisfied. For instance, small, lightweight secondary batteries with high capacity and high cycling stability are highly welcomed for the purpose of achieving both portability and long lifetime. At the same time, in the development of novel batteries, there is always an interest in being able to produce those batteries in an inexpensive manner.
Nowadays, sulfur has drawn people's attention for being used as cathode active material in lithium secondary batteries. By virtue of the low atomic weight of lithium and moderate weight of sulfur, Li—S batteries are relatively light, which are very promising in succeeding lithium-ion cells because of their higher energy density and the low cost of sulfur.
In order to achieve high-energy-density Li—S battery, many optimized categories of cathode technology and Li metal technology have been carried out to improve its electrochemical performances. Several problems need to be solved before sulfur cathode materials can be devoted to markets in rechargeable lithium batteries: (1) suitable particle size of sulfur should be achieved to ensure a high utilization rate of sulfur and then a high reversible capacity upon cycling; (2) discharge products of poly-sulfides should be carefully restrained from dissolving into the electrolyte to ensure a long cycle life; (3) the cathode material should have high ionic and electronic conductivities to ensure better rate performances.
So far, no lithium secondary battery with sulfur contained in its cathode material have yet truly succeeded in the market place due to various unsolved issues.
In light of the above, one of the objects of the present invention is to provide an electro-active material which is suitable for production of cathode materials for lithium secondary batteries, which successfully addresses the foregoing problems in the prior art. Further, another object of the present invention is to provide a method for realizing the sulfur-containing cathode material with those desired properties.
These objects are achieved by a sulfur-carbon composite material, said composite material comprising a porous carbon substrate containing both micropores and mesopores and sulfur, wherein the sulfur is only contained in the micropores of the carbon substrate.
According to another aspect of the present invention, there provides a lithium-sulfur battery comprising an anode, a cathode and an electrolyte medium, wherein said cathode comprising the sulfur-carbon composite material provided in the present invention.
According to yet another aspect of the present invention, there provides a method for preparing the sulfur-carbon composite material provided in the present invention, said method comprising: a) preparing precursor microporous carbon material; b) generating the porous carbon substrate containing both micropores and mesopores through the activation of the precursor microporous carbon material; and c) loading sulfur into the porous carbon substrate.
In this sulfur-carbon (S—C) composite material according to the present invention, the micropores can supply effective sulfur dispersion and store sulfur at even a molecular scale. On the other hand, the mesoporous structure with the continuous conductive network is beneficial to an efficient Li ion transportation. This way, the lithium-sulfur battery whose cathode is made from such S—C composite material as provided in the present invention may have at least one and especially more than one of the following properties: high specific capacity; high cycling stability; low self-discharge, good mechanical stability. Furthermore, the S—C composite materials are economically producible and of high reproducible quality, which facilitates the wide-spread application of the lithium secondary battery with sulfur contained in its cathode material.
The foregoing and other objects, features, and advantages of the invention will be apparent from the following more particular description of preferred embodiments as illustrated in the accompanying drawings, in which:
While the invention covers various modifications and alternative constructions, embodiments of the invention are shown in the drawings and will hereinafter be described in detail. However it should be understood that the specific description and drawings are not intended to limit the invention to the specific forms disclosed. On the contrary, it is intended that the scope of the claimed invention includes all modifications and alternative constructions thereof falling within the scope of the invention as expressed in the appended claims.
Unless defined in the context of the present description, otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The present invention is directed to a sulfur-carbon composite material which could be used as a cathode material for lithium secondary batteries. This specific composite material is composed of containing both micropores and mesopores and sulfur, where the sulfur is only contained in the micropores of the carbon substrate. As commonly known in the art, “micropores” refer to a pore size of less than 2 nm in term of diameter, whereas “mesopores” refer to a pore size of 2˜50 nm. In the present invention, the micropores preferably have an average diameter of 0.4-2 nm, more preferably 0.4-1.8 nm, while mesopores preferably have an average diameter of 3-8 nm. Besides, the porous carbon containing both micropores and mesopores may preferably have a Brunauer-Emmett-Teller (BET) specific area of 500-1500 m2/g and a total pore volume of 0.2-3.0 cm3/g. It is to be understand by those skilled in the art that the total pore volume and the pore size distribution within the carbon substrate can be adjusted through different preparation conditions. Preferably, within the porous carbon substrate, the micropores contributes to a larger percent of the total pore volume than the mesopores.
In the sulfur-carbon composite material according to the present invention, the sulfur is only contained in the micropores of the porous carbon substrate. That is to say, when this sulfur-carbon composite material is utilized in lithium-sulfur battery, all the effective (active) sulfur and the polysulfides and sulfide ions resulting from the electrochemical reaction will be accommodated by the micropores. In practice, though there may inevitably exist a minor portion of sulfur in the mesopores, they do not contribute to the charge-discharge process. In contrast, those mesopores mostly function to facilitate the efficient Li ion transportation during the electrochemical cycling. In general, an absolute majority of the sulfur is dispersed in those micropores.
For the sulfur-carbon composite material according to the present invention, there is no limit to the specific form of the sulfur used here. The amount of sulfur contained in the sulfur-carbon composite material can be adjusted, preferably within a range of 30-70 wt %.
Preferably, the sulfur to be loaded into the carbon substrate could be with chain structure, including small sulfur molecules S2-4 with short chain structures, S5-20 with chain structures, and polymeric sulfur S∞ with long chain structure, the diameter of which are less than the diameter of the micropores in the substrate.
In the sulfur-carbon composite material according to the present invention, the particular nanostructure of carbon substrate supporting sulfur exhibits a number of advantages as being used in the cathode of a lithium secondary battery. On one hand, the micropores can yield effective sulfur dispersion and store sulfur at even a molecular scale, and prevent the polysulfide dissolution so as to enable a much improved cycling performance. On the other hand, the mesoporous structure is beneficial to the efficient Li ion transportation. Besides, the carbon substrate with pores of different sizes has a continuous network with a high electronic conductivity to provide sufficient electrical contacts to the insulating sulfur. Therefore, its beneficial structure with a high specific surface area and a large pore volume contributes to a fast electrode reaction. All these merits lead to a sulfur carbon composite with high sulfur activity and utilization rate, fine cycling capacity and favorable rate capability in a lithium-sulfur battery.
Accordingly, a lithium-sulfur battery is provided. Typically, the lithium secondary batter according to the present invention may comprise an anode, a cathode and an electrolyte medium, where the cathode may comprise the above sulfur-carbon composite material.
For the lithium-sulfur battery according to the present invention, the electrolyte may preferably selected from the group of carbonate-based electrolyte, glyme-based electrolyte and the combination thereof with dissolved lithium salt. However, it is to be understand by those skilled in the art that there is no limit to the electrolyte used here.
A method for preparing this specific sulfur-carbon composite material is also provided in the present invention. Generally, the preparing process may comprise: a) preparing precursor microporous carbon material; b) generating the porous carbon substrate containing both micropores and mesopores through the activation of the precursor microporous carbon material; and c) loading sulfur into the porous carbon substrate.
In one embodiment of the present invention, pyrolysis microporous carbon spheres (MPCSs) with a diameter of 50 nm-20 μm are yielded as the precursor material to produce the supporting carbon substrate for sulfur with both micropores and mesopores contained therein. The diameter of MSPCS can be tuned ranging from 150-500 nm under different preparation conditions. In this case, a hydrothermal reaction of carbohydrate may be conducted to produce MSPCSs. Carbon sources for the generation of MPCSs for example can include carbohydrates, such as sucrose, D-glucose, fructose and other carbohydrates or any combinations thereof. Surfactants for this hydrothermal reaction can for example include anionic surfactant, such as sodium dodecyl benzene sulfonate (SDBS), oleic acid, sodium lauryl sulfonate (SLS), sodium dodecyl sulfate (SDS), cationic surfactant, such as cetyl trimethyl ammonium bromide, and nonionic surfactant, such as polyvinyl pyrrolidone (PVP), Tween-40, Tween-80.
For example, the hydrothermal reaction could include: i) dissolving 2-8 g of D-glucose in 20-60 ml of water; ii) sealing the solution in an autoclave and making it react at 150° C. to 200° C. for 2 h to 12 h to initially yield MPCSs; iii) centrifuging the products and washing them with water or ethanol for several times; and iv) drying the products at 50° C. in an oven to obtain the original MPCSs.
In the preparation method according to the present invention, the activation of the precursor microporous carbon material may comprise: i) dispersing the precursor microporous carbon material in aqueous solution of potassium hydroxide (KOH); ii) filtrating the microporous carbon material with a complete adsorption of KOH in its micropores; and iii) removing the KOH contained in the filtrated microporous carbon material through carbonization to obtain the porous carbon substrate containing both micropores and mesopores.
When MPCSs are used as the precursor material to produce the supporting carbon substrate, activation of the MPCSs could include dispersing 50-400 mg of the MPCSs in 2.5-40 ml of aqueous solution of potassium hydroxide (KOH). To ensure an appropriate pore size distribution within the MPCSs, the concentration of KOH could preferably be adjusted to 0.1-10 mol/L, which facilitates the proper distribution of both micropores and mesopores with a MSPCS. For this preparation process, the pore size distribution substantially depends on the concentration of the activation solution. The suspension containing the MPCSs could then experience a sonicating of 2 h to 8 h, standing for 10 h to 48 h to enable a complete adsorption of KOH in those original micropores before filtration. The filtrated MPCSs could be dried at 50° C. in an oven, and then annealed at 700-1000° C. in an inert gas (such as nitrogen, argon, etc.) for 2 h to 4 h with a heating rate of 2-10° C./min to further carbonize the MPCSs. To ensure a complete removal of KOH, the resulting sample after carbonization is washed continuously with de-ionized water until the pH of the filtrate becomes 7. Thus, the activated MPCSs may be used as the porous carbon substrate in the sulfur-carbon composite material according to the present invention.
In the preparation method according to the present invention, the process for loading sulfur may comprise: yielding a homogeneous mixture of sulfur and the porous carbon substrate; and heating the mixture in a sealed container to make sulfur dispersed into the micropores within the porous carbon substrate.
In the case of MPCSs, Loading of sulfur into the supporting porous carbon structure could include mixing sulfur and the activated MPCSs by an appropriate mass ratio, such as mS:mC of 1:2 to 2:1, in a quartz mortar to yield a homogeneous mixture. After that, the mixture could be sealed in a glass container and heated at 130-170° C. for 5-20 h to make sulfur dispersed into the composite, especially into the micropores.
To prepare the precursor microporous carbon material, 4.5 g of D-glucose and 30 mg sodium dodecyl sulfate (SDS) were added into 30 ml of water in step 11. The solution was then sealed in an autoclave and heated at 180° C. for 4 h to yield the microporous carbon spheres as precursor material for the specific carbon substrate according to the present invention. The MPCSs were washed with de-ionized water for several times and dried in an oven overnight.
To prepare the porous carbon substrate containing both micropores and mesopores, 100 mg of MPCSs were mixed with 5 mL of 1 mol/L of KOH solution in step 12. The mixture were sonicated for 4 h, standing for 20 h, and then filtrated and dried in an oven for overnight. In step 13, the MPCSs which have absorbed sufficient potassium hydroxide solution were annealed at 800° C. in an inert gas (such as nitrogen, argon etc.) for 1 h with a heating rate of 5° C./min for further carbonization.
The final activated MPCSs were with an average diameter of 350 nm, a BET surface area of 827.871 m2/g and a total pore volume of 0.608 cm3/g. Test for this bimodal micropore distribution, such as NLDFT adsorption shows a smaller size of micropores of about 0.465 nm in diameter and larger micropores of 1.63 nm. The average mesopore diameter is about 3.8 nm, and the total mesopore volume of the MPCS is 0.25 cm3/g.
To yield the sulfur-carbon composite according to the present invention, sulfur and the carbon substrate were mixed by an mass ratio of 1:1 in a quartz mortar to yield a homogeneous mixture in step 14. The mixture was then sealed in a glass container and heated at 155° C. for 20 h to make sulfur dispersed into the carbon substrate so as to yield the sulfur-carbon composite.
According to the results of pore size distribution analysis, slit/cylinder pore, NLDFT equilibrium model fitting exhibits smallest deviation for the activated MPCS; while slit pore, QSDFT equilibrium model fitting shows the smallest deviation for the later S-MPCS composite with a sulfur loading of 40 weight percent (wt %), also as shown in
As shown in
It is to be noted that
To prepare the precursor microporous carbon material, 5 g of sucrose and 20 mg sodium dodecyl sulfate (SDS) were added into 40 mL of water. The solution was then sealed in an autoclave and heated at 180° C. for 6 h to yield the microporous carbon spheres as precursor material for the specific carbon substrate according to the present invention. MPCS were centrifuged with de-ionized water for several times and dried in an oven overnight.
To prepare the porous carbon substrate containing both micropores and mesopores, 400 mg of as-obtained MPCS were mixed with 10 mL of 0.75 mol/L of KOH solution. The mixture were sonicated for 2 h, stood for 10 h, and then filtrated and dried in an oven for overnight. After that, the MPCSs which have absorbed sufficient potassium hydroxide solution were further annealed at 800° C. in an inert gas (such as nitrogen, argon, etc.) for 2 h with a heating rate of 2° C./min to further carbonization. The final MPCS was with an average diameter of 500 nm and a total pore volume of 0.75 cm3/g, a BET surface area of 593.183 m2/g, the micropores of about 0.532 nm in diameter and larger micropores of 1.71 nm. The average mesopore diameter is about 2.8 nm, and the total mesopore volume of the MPCS is 0.5 cm3/g.
To yield the sulfur-carbon composite according to the present invention, sulfur and the carbon substrate were mixed by a mass ratio of 1:2 in a quartz mortar to yield a homogeneous mixture. The mixture was then sealed in a glass container and heated at 160° C. for 20 h to make sulfur dispersed into the carbon substrate so as to yield the sulfur-carbon composite.
When discharged at a rate of 0.1 C, the sulfur-carbon composite as obtained in embodiment B demonstrated a first discharge capacity of 501.6 mA h/g and reversible capacity up to 281.5 mA h/g calculated based on the mass of sulfur-carbon composite, utilization of the active material being 50.4%.
To prepare the precursor microporous carbon material, 5 g of sucrose and 20 mg sodium dodecyl sulfate (SDS) were added into 40 mL of water. The solution was then sealed in an autoclave and heated at 180° C. for 10 h to yield the microporous carbon spheres as precursor material for the specific carbon substrate according to the present invention. MPCS were centrifuged with de-ionized water for several times and dried in an oven overnight.
To prepare the porous carbon substrate containing both micropores and mesopores, 400 mg of as-obtained MPCS were mixed with 10 mL of 8 mol/L of KOH solution. The mixture were sonicated for 2 h, stood for 10 h, and then filtrated and dried in an oven for overnight. After that, the MPCSs which have absorbed sufficient potassium hydroxide solution were further annealed at 800° C. in an inert gas (such as nitrogen, argon, etc.) for 2 h with a heating rate of 2° C./min to further carbonization. The final MPCS was with an average diameter of 1 μm and a total pore volume of 1.141 cm3/g, a BET surface area of 1474.427 m2/g, the micropores of about 0.451 nm in diameter and larger micropores of 1.06 nm. The average mesopore diameter is about 3.29 nm, and the total mesopore volume of the MPCS is 0.845 cm3/g.
To yield the sulfur-carbon composite according to the present invention, sulfur and the carbon substrate were mixed by a mass ratio of 2:3 in a quartz mortar to yield a homogeneous mixture. The mixture was then sealed in a glass container and heated at 160° C. for 20 h to make sulfur dispersed into the carbon substrate so as to yield the sulfur-carbon composite.
When discharged at a rate of 0.1 C, the sulfur-carbon composite as obtained in embodiment C demonstrated a first discharge capacity of 408.4 mA h/g and reversible capacity up to 149.08 mA h/g calculated based on the mass of sulfur-carbon composite, utilization of the active material being 22.2%.
The present invention provides a sulfur-carbon cathode materials with good stability and rate capacity. Such material can be readily used in Li—S battery. The lithium secondary batteries using this kind of material in its cathode may have acceptable high power density for energy storage applications, such as power tools, photovoltaic cells and electric vehicles.
It should be noted that the aforesaid embodiments are illustrative of this invention instead of restricting it, substitute embodiments may be designed by those skilled in the art without departing from the scope of the claims below. The wordings such as “include”, “including”, “comprise” and “comprising” do not exclude elements or steps which are present but not listed in the description and the claims. It also shall be noted that as used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. This invention can be achieved by means of hardware including several different elements or by means of a suitably programmed computer. In the unit claims that list several means, several ones among these means can be specifically embodied in the same hardware item. The use of such words as first, second, third does not represent any order, which can be simply explained as names.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2012/085898 | 12/5/2012 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2014/085992 | 6/12/2014 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20110052998 | Liang et al. | Mar 2011 | A1 |
| 20130065127 | Nazar | Mar 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| 2012100301 | Aug 2012 | WO |
| 2012149672 | Nov 2012 | WO |
| Entry |
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| International Search Report corresponding to PCT Application No. PCT/CN2012/085898, dated Sep. 12, 2013 (3 pages). |
| Ji X et al: “A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries”, Nature Materials, Nature Publishing Group, GB, vol. 8, No. 6, Jun. 1, 2009, pp. 500-506, XP002569830. |
| B. Zhang et al: “Enhancement of long stability of sulfur cathode by encapsulating sulfur into micropores of carbon spheres”, The Royal Society of Chemistry, 2010, vol. 3, pp. 1531-1537. |
| Number | Date | Country | |
|---|---|---|---|
| 20150303458 A1 | Oct 2015 | US |
