CN110676338B - Solar energy-assisted energy-saving rechargeable organic lithium-sulfur battery - Google Patents
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000007600 charging Methods 0.000 claims abstract description 39
- 239000004065 semiconductor Substances 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229920001021 polysulfide Polymers 0.000 claims abstract description 9
- 239000005077 polysulfide Substances 0.000 claims abstract description 9
- 150000008117 polysulfides Polymers 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910002367 SrTiO Inorganic materials 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000010325 electrochemical charging Methods 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000002073 nanorod Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002135 nanosheet Substances 0.000 claims description 7
- 239000002071 nanotube Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 13
- 238000005286 illumination Methods 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910052950 sphalerite Inorganic materials 0.000 description 20
- 229910052984 zinc sulfide Inorganic materials 0.000 description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- ZNJRWJSLGMRLAZ-UHFFFAOYSA-N C1(CCC(N1)=O)=O.[Li].FC(F)F.FC(F)F Chemical compound C1(CCC(N1)=O)=O.[Li].FC(F)F.FC(F)F ZNJRWJSLGMRLAZ-UHFFFAOYSA-N 0.000 description 2
- 229910007552 Li2Sn Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal sulfide Chemical class 0.000 description 2
- 229910003003 Li-S Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- QNIHZKIMYOTOTA-UHFFFAOYSA-N fluoroform;lithium Chemical compound [Li].FC(F)F.FC(F)F QNIHZKIMYOTOTA-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
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- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/053—Energy storage means directly associated or integrated with the PV cell, e.g. a capacitor integrated with a PV cell
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of conversion and storage from solar energy to electric energy, in particular to a solar energy-assisted energy-saving rechargeable organic lithium-sulfur battery. The solar auxiliary charging organic lithium-sulfur battery comprises a solid sulfur or polysulfide ion solution positive electrode, a lithium negative electrode and a semiconductor photoelectrode. When the solar photovoltaic battery is charged by illumination, a semiconductor photoelectrode is excited by light to generate photogenerated electrons and holes, the holes in a valence band oxidize polysulfide ions, the photogenerated electrons reduce metal lithium through an external circuit, the photovoltage generated by the photoelectrode partially compensates charging voltage, the charging voltage is reduced, the purpose of saving electric energy is achieved, and meanwhile conversion and storage from solar energy to electric energy are achieved. The invention provides a high-efficiency stable solar rechargeable lithium-sulfur battery, which is simple in preparation method, mild in process conditions and low in cost, and meets the requirements of industrial production.
Description
Technical Field
The invention relates to the field of conversion and storage from solar energy to electric energy, in particular to a solar energy-assisted energy-saving rechargeable organic lithium-sulfur battery.
Background
Efficient storage and utilization of solar energy is one of the effective ways to alleviate the energy crisis and environmental pollution problems currently facing the world. The construction of efficient solar rechargeable batteries is a new trend in the field of energy storage. The solar rechargeable lithium ion battery is divided into two types according to the construction mode: 1) the photovoltaic cell integrated battery integrates a photovoltaic cell (including a dye-sensitized solar cell or a perovskite solar cell) into a traditional lithium ion battery or a capacitor, and the photovoltaic cell converts solar energy into electric energy to charge the battery or the capacitor in the illumination process. The discharge capacity of such devices reported to date is low, such as: the discharge capacity of the light rechargeable battery reported by Guo et al [12] is only 38.89 mu Ah, and the discharge capacity can not reach the capacity level of a commercial lithium ion battery, and can not meet the requirement of solar energy mass storage (W.X.Guo, X.Y.Xue, S.H.Wang, C.J.Lin, Z.L.Wang.Nano Lett.2012,12,2520). In addition, because the voltage of the solar photovoltaic cell is low, 4-10 solar photovoltaic cells are often required to be connected in series to meet the charging voltage of the lithium ion battery, the weight of the device is increased, the portability is reduced, and the technical difficulty and the processing cost of the device are increased; 2) a photoelectrode-implanted battery, Yu in the united states, etc., constitutes a novel photoelectrode-implanted solar-assisted rechargeable battery, and its structure is simpler than the former (m.z.yu, x.d.ren, l.ma, y.y.wu. _ nat. commun.2014,5,5111). A semiconductor photoelectrode with a proper band edge position is implanted into a battery system, and when the photoelectrode is illuminated, the photoelectrode absorbs photons with energy higher than a band gap, electrons in a valence band are excited to a conduction band, and holes are generated in the valence band. The positive electrode material adsorbed on the surface of the material is oxidized by the diffusion of holes in the valence band to the surface of the material, and the negative electrode material is reduced by the diffusion of electrons on the conduction band to the negative electrode through an external circuit under the assistance of voltage. In the process, the photovoltage generated by the photoelectrode compensates for part of the charging voltage, thereby reducing the charging voltage. The input of electric energy can be saved when the battery is charged by simply introducing the photoelectrode, the conversion and the storage of solar energy to electric energy are indirectly realized, and a new thought is provided for designing and developing novel high-efficiency solar rechargeable batteries.
The lithium-sulfur battery is a novel high-capacity energy storage system with great development prospect, has the outstanding advantages of high theoretical energy density, low cost, environmental protection and the like, and shows wide application prospect in the emerging technical fields of power batteries for new energy automobiles and the like. The theoretical specific capacity of the lithium-sulfur battery is up to 1675mAh g-1The theoretical specific energy density of the constructed lithium secondary battery system can reach 2600Wh kg-1The lithium-sulfur battery is 3-5 times of the current commercial lithium-ion battery, so that the development of the solar rechargeable lithium-sulfur battery is an effective means for realizing the mass conversion and storage of solar energy. Through careful analysis of research progress in related fields at home and abroad, few researches on solar-charged lithium-sulfur batteries are carried out so far, and the only report is that a biliquid lithium-sulfur battery capable of converting and storing solar energy is proposed in the early stage. However, when the battery is charged by illumination, the photo-generated electrons are not transferred to the negative electrode to reduce lithium ions into metal lithium, but protons are reduced into hydrogen, so that conversion and storage from solar energy to chemical energy are realized, and the metal lithium is continuously consumed while the solar energy is stored. In addition, the two-liquid system requires Li1.35Ti1.75Al0.25P2.7Si0.3O12The (LATP) ceramic diaphragm isolates a water system anode and an organic system cathode, and has the problems of high cost and potential safety hazard.
Disclosure of Invention
The invention aims to provide a solar auxiliary energy-saving charging type organic lithium sulfur battery, which is constructed by implanting a semiconductor photoelectrode into a positive electrode of the lithium sulfur battery so as to realize mass storage of solar energy in the lithium sulfur battery.
The technical scheme of the invention is as follows:
a solar energy auxiliary energy-saving charging type organic lithium sulfur battery is formed by taking metal lithium as a negative electrode, taking solid sulfur or polysulfide ion solution as a positive electrode, taking a photoelectrode as a semiconductor photoelectrode material and taking ether solution containing lithium salt as electrolyte.
The anode of the solar energy auxiliary energy-saving charging type organic lithium-sulfur battery is solid sulfur, lithium sulfide and Li2Sn(1<n<8) Or a composite thereof.
According to the solar energy-assisted energy-saving rechargeable organic lithium-sulfur battery, the positive electrode composite material comprises a carbon material, an organic polymer or a transition metal sulfide material.
The solar energy-assisted energy-saving rechargeable organic lithium-sulfur battery is characterized in that the electrolyte is an organic ether electrolyte containing bis (trifluoromethane) lithium succinimide, the molar concentration of the bis (trifluoromethane) lithium succinimide is 1-10M, and the organic ether comprises ethylene glycol dimethyl ether, dimethyl sulfoxide, tetrahydrofuran, dioxolane or tetraethylene glycol dimethyl ether.
The solar energy auxiliary energy-saving rechargeable organic lithium sulfur battery has the photoelectrode material of ZnS, CdS and C3N4、SrTiO3Or TiO2。
The solar energy auxiliary energy-saving rechargeable organic lithium sulfur battery has a photoelectrode base material of Ti, Al, Cu, ITO or FTO.
The design idea of the invention is as follows:
the invention firstly passes throughThe solar energy is assisted to save the electric energy required by charging the lithium-sulfur battery, when the lithium-sulfur battery is charged by illumination, a semiconductor photoelectrode is excited by light to generate photoproduction electrons and holes, and the holes in a valence band are diffused to the surface of the semiconductor to enable S2-(or S)4 2-) Ions are oxidized into polysulfide ions, and photo-generated electrons are diffused to the lithium cathode through an external circuit under the assistance of external voltage to reduce the lithium ions into metallic lithium. In the process, the photogenerated voltage generated by the photo-excited semiconductor photoelectrode partially compensates the voltage in the charging process, so that the electric energy required by charging is saved, and the conversion and storage of solar energy are indirectly realized.
The invention has the advantages and beneficial effects that:
1. the key point of the invention is that the photoelectric electrode is introduced into the anode of the traditional lithium-sulfur battery to save the charging point electric energy of the lithium-sulfur battery, when the battery is charged by illumination, the semiconductor photoelectric electrode is excited by light to generate photoproduction electrons and holes, the holes in the valence band oxidize polysulfide ions, and the photoproduction electrons reduce metal lithium through an external circuit, and the photoelectric electrode is simply introduced to save the electric energy input when the battery is charged, thereby providing reference for designing and developing novel high-efficiency solar rechargeable batteries.
2. The invention realizes the direct conversion and storage of solar energy in the large-scale energy storage device lithium sulfur battery and provides guidance for the reasonable utilization of novel renewable energy sources.
Drawings
FIG. 1 is a schematic structural diagram of a solar-assisted energy-saving rechargeable organic lithium-sulfur battery.
Fig. 2 is a graph of the photo-assisted charging and electrochemical charging contrast for a ZnS-based photo-assisted rechargeable battery, wherein: curve 1 represents an Electrochemical charge (Electrochemical charge) curve, and curve 2 represents a Photo-charged (Photo-assisted charge) curve; in the figure, the abscissa Time represents Time (min) and the ordinate Voltage represents Voltage (V).
FIG. 3 Scanning (SEM) picture of ZnS.
Fig. 4 XRD picture of ZnS. In the figure, the abscissa 2 θ represents the diffraction angle (degree), the ordinate Intensity represents the relative Intensity (a.u.), Sphalerite ZnS represents Sphalerite, and Wurtzite ZnS represents Wurtzite.
FIG. 5 SrTiO3XRD pictures of (a). In the figure, the abscissa 2Theta represents a diffraction angle (°), and the ordinate Intensity represents a relative Intensity (a.u ℃).
FIG. 6 growth of TiO on carbon paper2SEM pictures of nanoplatelets.
FIG. 7 growth of TiO on carbon paper2SEM pictures of nanorods.
FIG. 8 TiO growth on titanium mesh2SEM pictures of nanotubes.
FIG. 9 shows SrTiO3A ZnS-based photo-assisted charging and electrochemical charging contrast curve for a photo-electrode, wherein: curve 1 represents TiO2The curve of photo-charging of the nanorod template, curve 2 represents TiO2The nano-sheet template photo-charging curve, and curve 3 represents the electrochemical charging curve. In the figure, the abscissa Time represents Time (min) and the ordinate Voltage represents Voltage (V).
Detailed Description
In the specific implementation process, the invention relates to a solar energy auxiliary energy-saving charging type organic lithium-sulfur battery, which comprises a solid sulfur or polysulfide ion solution positive electrode, a lithium negative electrode and a semiconductor photoelectrode, wherein the semiconductor photoelectrode is implanted into the positive electrode of the lithium-sulfur battery to construct the solar energy auxiliary charging type organic lithium-sulfur battery so as to realize mass storage of solar energy in the lithium-sulfur battery. During charging by illumination, the semiconductor photoelectrode is excited by light to generate photo-generated electrons and holes, and the holes in the valence band diffuse to the surface of the semiconductor to form S2-(or S)4 2-) Ions are oxidized into polysulfide ions, and photo-generated electrons are diffused to the lithium cathode through an external circuit under the assistance of external voltage to reduce the lithium ions into metallic lithium. The method comprises the following specific steps:
1. the positive electrode is solid sulfur, lithium sulfide or Li2Sn(1<n<8) And composites thereof, the composites comprising a carbon material, an organic polymer or a transition metal sulfide material.
2. The organic electrolyte is an organic ether electrolyte of lithium bistrifluoromethane yellow imide with the molar concentration of 1-10M, and the organic ether comprises ethylene glycol dimethyl ether, dimethyl sulfoxide, tetrahydrofuran, dioxolane or tetraethylene glycol dimethyl ether.
3. The photoelectrode material is ZnS, CdS, C3N4、SrTiO3Or TiO2The preparation method comprises hydrothermal, anodic oxidation or magnetron sputtering and the like.
4. The photoelectrode base material is Ti, Al, Cu, ITO or FTO.
The present invention will be described in further detail with reference to the following examples and the accompanying drawings.
Example 1
In this example, zinc nitrate and thiourea were first dissolved in deionized water to prepare 35ml, 0.03mol/L zinc nitrate solution and 35ml, 0.03mol/L thiourea solution, and the thiourea solution was added to the zinc nitrate solution and stirred for 30 minutes to be clear. And then transferring the mixed solution into the inner liner of a hydrothermal reaction kettle, heating to 140 ℃, reacting for 8 hours at the temperature, naturally cooling to room temperature after the reaction is finished, taking out, and sequentially performing centrifugal washing by using deionized water and absolute ethyl alcohol. And finally, drying the ZnS particles in a drying oven at the temperature of 60 ℃ for 4 hours to obtain spherical ZnS particles with the size of 200-300 nanometers.
As shown in fig. 1, the light-assisted rechargeable lithium-sulfur battery structure includes a lithium sheet, a diaphragm, a sulfur composite electrode, and a semiconductor photoelectrode material, which are vertically and parallelly disposed in an electrolyte, and the metal lithium sheet is used as a negative electrode, the sulfur composite electrode is used as a positive electrode, the semiconductor photoelectrode material disposed outside the sulfur composite electrode is used as a photoelectrode, hv is the energy of incident photons, an ether solution containing lithium salt (electrolyte) is used as an electrolyte, the composition of the sulfur composite electrode in the embodiment is sulfur powder and ketjen black, wherein the mass ratio of the sulfur powder to the ketjen black is 8: 2, the diaphragm material between the metal lithium sheet and the sulfur composite electrode is a PP diaphragm to form the solar auxiliary energy-saving rechargeable organic lithium sulfur battery, and the oxidation-reduction reaction of active substances and the working principle of a photoelectrode during charging and discharging of the ZnS-based photo-auxiliary rechargeable battery are shown as follows: in the photo-assisted charging process, the semiconductor photoelectrode material absorbs incident light to generate photo-generated electrons and photo-generated holes, the photo-generated holes participate in an oxidation reaction on the surface of the photoelectrode, and the photo-generated electrons are transmitted to the negative electrode through the current collector and the wire to participate in a reduction reaction.
As shown in FIG. 2, the ZnS-based photo-assisted rechargeable batteryCharging and electrochemical charging (i.e., charging in the dark) versus curves. The voltage plateau of electrochemical charging of the ZnS-based photo-assisted rechargeable battery is 2.48V, and the voltage plateau of photo-assisted charging is 1.87V; the visible light-assisted charging effectively reduces the charging voltage of the battery. When charged under light irradiation, S2-Ions are oxidized to S by photo-excited holes6 2-Ions; at the same time, electrons generated by light excitation are transferred to the negative electrode through an external circuit, and Li is transferred+Reducing the metal into metal. Therefore, the charging voltage of the Li-S battery is compensated by the photo-voltage generated by the photo-electrode, so that the charging voltage is lowered.
As shown in FIG. 3, the SEM picture of ZnS shows that the prepared ZnS particles are in an incompletely regular spherical shape with the diameter of 200-300 nm, and certain adhesion exists among the particles.
As shown in FIG. 4, the XRD picture of ZnS shows that the prepared ZnS particles have low crystallinity and small grain size and are a binary mixed phase of sphalerite and wurtzite crystals.
Example 2
In this example, TiO is used2Preparation of SrTiO for precursor3The photoelectrode comprises the following specific processes:
1. preparation of TiO of different morphologies2Precursor:
(1) growing TiO on carbon paper2Nanosheet: adding 30 mu l of Diethylenetriamine (DETA) into 42ml of isopropanol, stirring for 5 minutes, adding 1.5ml of titanium isopropoxide, stirring for 10 minutes, transferring the mixed solution into the inner liner of a hydrothermal reaction kettle, putting carbon paper into the inner liner of the reaction kettle, heating to 200 ℃, keeping the temperature for 24 hours, naturally cooling to room temperature after the reaction is finished, taking out the carbon paper, and adding absolute ethyl alcohol for centrifugal washing; finally, the carbon paper is put into a 60 ℃ oven to be dried for 12 hours, and TiO with the white color and the thickness of about 20 nanometers which uniformly grows on the carbon paper is obtained2Nanosheets.
(2) Growing TiO on carbon paper2And (3) nano-rods: solution 1: 0.45ml of Tetraisopropyl Titanate (TTIP) was added to 2ml of glycerol and stirred well. Solution 2: 0.893g of ethylenediaminetetraacetic acid disodium salt (Na)2EDTA) was added to 38ml of deionized water. In the process of continuously stirring, dropwise adding the solution 1 into the solution 2 to obtain a mixed solution, placing the mixed solution in an electric heating sleeve, heating at 70 ℃ for 1 hour, transferring the mixed solution into a lining of a hydrothermal reaction kettle, placing carbon paper into the lining of the reaction kettle, heating to 200 ℃, reacting at the temperature for 5 hours, naturally cooling to room temperature after the reaction is finished, taking out the carbon paper, sequentially carrying out centrifugal washing by deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours. Finally, the carbon paper is placed in a muffle furnace and heated for 1 hour at 450 ℃, and TiO with white color and 200-300 nanometer particle size, which uniformly grows on the carbon paper, is obtained2And (4) nanorods.
(3) Growing TiO on titanium mesh2Nanotube: 10ml of deionized water, 90ml of ethylene glycol, 0.548mg of ammonium fluoride (NH) were added to a beaker4F) Stirring evenly to obtain a mixed solution, and immersing the titanium mesh in the solution for anodic oxidation. The initial voltage is 30V, the voltage is changed to 20V after 30 minutes, the cycle is carried out, and the anodic oxidation time is 6 hours. Taking out, sequentially carrying out centrifugal washing by deionized water and alcohol, and drying for 12 hours at 60 ℃. Finally, the titanium net is put in a muffle furnace to be heated to 550 ℃ and heated for 2 hours at the temperature, and TiO with white color and particle size of about 50 nanometers uniformly grown on the titanium net is obtained2A nanotube.
2. Preparation of SrTiO by hydrothermal reaction3：
5ml of deionized water and 35ml of ethylene glycol were added to a beaker and stirred well to form a solution. To the above solution, 2mmol of sodium hydroxide was added with stirring. Stirring for 10 min, adding strontium nitrate, and adding TiO2The mass ratio of (A) to (B) is 1: 2. Stirring for 30 min, transferring the solution to high-pressure reactor, and adding TiO2Nanosheets or TiO2Carbon paper or growing TiO of nano-rod precursor2The titanium mesh of nanotubes was subjected to hydrothermal reaction at 170 ℃ for 6 hours. The sample was taken out, rinsed with deionized water and alcohol, and dried at 60 ℃ for 12 hours. Putting the dried sample into a tube furnace, carrying out heat treatment at 700 ℃ for 4 hours in Ar atmosphere at the heating rate of 2 ℃/min, and carrying out heat treatment on the sample after heat treatmentSoak in acetic acid for 24 hours.
As shown in FIG. 5, SrTiO3The XRD picture shows that the prepared SrTiO is compared with the standard spectrum3Has a lower characteristic diffraction peak, SrTiO3Less content, low crystallinity and small grain size.
As shown in FIG. 6, TiO2SEM picture of (B) shows that the prepared TiO2Is in the form of uniform sheet.
As shown in FIG. 7, TiO2SEM picture of (B) shows that the prepared TiO2Is in the shape of a uniform rod.
As shown in FIG. 8, TiO2SEM picture of (B) shows that the prepared TiO2Is in a uniform tubular shape.
As shown in FIG. 9, with SrTiO3As a photoelectrode, the photo-assisted charging and electrochemical charging (i.e., charging in the dark) of a battery are contrasted. SrTiO3The electrochemical charging voltage platform of the photo-assisted rechargeable battery is 2.48V and is in the form of flake TiO2Prepared SrTiO for template3When used as a photoelectrode, the charging voltage plateau is 2.23V. In the form of rod TiO2Prepared SrTiO for template3When used as a photoelectrode, the charging voltage plateau was 2.19V. Therefore, the light-assisted charging effectively reduces the charging voltage of the battery.
The embodiment results show that the invention constructs a high-efficiency and stable solar-assisted energy-saving rechargeable organic lithium-sulfur battery, when in illumination charging, a semiconductor photoelectrode is excited by light to generate photo-generated electrons and holes, and the holes in a valence band are diffused to the surface of a semiconductor to form S2-(or S)4 2-) Ions are oxidized into polysulfide ions, and photo-generated electrons are diffused to the lithium cathode through an external circuit under the assistance of external voltage to reduce the lithium ions into metallic lithium. In the process, the photogenerated voltage generated by the photo-excited semiconductor photoelectrode partially compensates the voltage in the charging process, so that the electric energy required by charging is saved, and the conversion and storage of solar energy are indirectly realized. The preparation method is simple, mild in process conditions and low in cost, and meets the requirements of industrial production.
Claims (1)
1. A solar energy-assisted energy-saving rechargeable organic lithium-sulfur battery is characterized in that metal lithium is used as a negative electrode, solid sulfur or polysulfide ion solution is used as a positive electrode, the photoelectrode is a semiconductor photoelectrode material, and ether solution containing lithium salt is used as electrolyte to form the solar energy-assisted energy-saving rechargeable organic lithium-sulfur battery;
with TiO2Preparation of SrTiO for precursor3The photoelectrode comprises the following specific processes:
(1) preparation of TiO of different morphologies2Precursor:
1) growing TiO on carbon paper2Nanosheet: adding 30 mu l of diethylenetriamine DETA into 42ml of isopropanol, stirring for 5 minutes, adding 1.5ml of titanium isopropoxide, stirring for 10 minutes, transferring the mixed solution into the inner liner of a hydrothermal reaction kettle, putting carbon paper into the inner liner of the reaction kettle, heating to 200 ℃, keeping the temperature for 24 hours, naturally cooling to room temperature after the reaction is finished, taking out the carbon paper, and adding absolute ethyl alcohol for centrifugal washing; finally, the carbon paper is put into a 60 ℃ oven to be dried for 12 hours, and the white TiO with the thickness of 20 nanometers which is uniformly grown on the carbon paper is obtained2Nanosheets;
2) growing TiO on carbon paper2And (3) nano-rods: solution 1: adding 0.45ml of tetraisopropyl titanate TTIP into 2ml of glycerol, and uniformly stirring; solution 2: 0.893g of disodium ethylenediaminetetraacetate Na salt2EDTA was added to 38ml of deionized water; in the process of continuously stirring, dropwise adding the solution 1 into the solution 2 to obtain a mixed solution, placing the mixed solution in an electric heating sleeve, heating at 70 ℃ for 1 hour, transferring the mixed solution into a lining of a hydrothermal reaction kettle, placing carbon paper into the lining of the reaction kettle, heating to 200 ℃, reacting at the temperature for 5 hours, naturally cooling to room temperature after the reaction is finished, taking out the carbon paper, sequentially carrying out centrifugal washing by deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours; finally, the carbon paper is placed in a muffle furnace and heated for 1 hour at 450 ℃, and TiO with white color and 200-300 nanometer particle size, which uniformly grows on the carbon paper, is obtained2A nanorod;
3) growing TiO on titanium mesh2Nanotube: 10ml of deionized water was added to the beaker90ml of ethylene glycol, 0.548mg of ammonium fluoride NH4F, uniformly stirring to obtain a mixed solution, and soaking a titanium mesh in the solution for anodic oxidation; the initial voltage is 30V, the voltage is changed to 20V after 30 minutes, the cycle is carried out, and the anodic oxidation time is 6 hours; taking out, sequentially carrying out centrifugal washing by using deionized water and alcohol, and drying for 12 hours at 60 ℃; finally, the titanium mesh is put in a muffle furnace to be heated to 550 ℃ and heated for 2 hours at the temperature, and TiO with white color and 50 nm particle size uniformly grown on the titanium mesh is obtained2A nanotube;
(2) preparation of SrTiO by hydrothermal reaction3：
Adding 5ml of deionized water and 35ml of ethylene glycol into a beaker, and uniformly stirring to form a solution; adding 2mmol of sodium hydroxide into the solution under the stirring state; stirring for 10 min, adding strontium nitrate, and adding TiO2The mass ratio of (A) to (B) is 1: 2; stirring for 30 min, transferring the solution to high-pressure reactor, and adding TiO2Nanosheets or TiO2Carbon paper or growing TiO of nano-rod precursor2Carrying out hydrothermal reaction on the titanium mesh of the nanotube for 6 hours at the temperature of 170 ℃; taking out the sample, washing with deionized water and alcohol, and drying at 60 ℃ for 12 hours; putting the dried sample into a tubular furnace, carrying out heat treatment at 700 ℃ for 4 hours in Ar atmosphere at the heating rate of 2 ℃/min, and soaking the sample subjected to heat treatment for 24 hours by using acetic acid;
with SrTiO3When used as photoelectrode, SrTiO3The electrochemical charging voltage platform of the photo-assisted rechargeable battery is 2.48V and is in the form of flake TiO2Prepared SrTiO for template3When the photoelectric cell is used as a photoelectrode, the charging voltage platform is 2.23V; in the form of rod TiO2Prepared SrTiO for template3When used as a photoelectrode, the charging voltage plateau was 2.19V.
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