CN114639878A - Aqueous lithium ion battery electrolyte based on oligomer and application thereof - Google Patents
Aqueous lithium ion battery electrolyte based on oligomer and application thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 142
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229930192474 thiophene Natural products 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 238000012983 electrochemical energy storage Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 32
- 239000008151 electrolyte solution Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 21
- 230000014759 maintenance of location Effects 0.000 description 20
- 238000000034 method Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000011149 active material Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 8
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000004832 voltammetry Methods 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 239000005486 organic electrolyte Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 125000000168 pyrrolyl group Chemical group 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013179 LiNixCo1-xO2 Inorganic materials 0.000 description 1
- 229910013171 LiNixCo1−xO2 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
Abstract
The invention discloses an aqueous lithium ion battery electrolyte based on oligomer, which comprises oligomer solute, electrolyte and water; wherein the oligomeric solute is selected from oligomers of pyrrole, aniline or thiophene; the electrolyte is a lithium-containing soluble salt. The electrolyte has the characteristics of high voltage window and good cycling stability, and is suitable for high-pressure water system lithium ion batteries. The invention also discloses application of the electrolyte.
Description
Technical Field
The present invention relates to the field of aqueous ion batteries. More particularly, to an oligomer-based aqueous lithium ion battery electrolyte and applications thereof.
Background
Although commercial lithium ion batteries have many advantages such as high energy density, high cycling stability and high energy efficiency, the use of organic electrolytes with high cost and poor safety still prevents large-scale energy storage application. In view of this, development of an aqueous electrolyte with high safety factor, easy preparation and high ionic conductivity is an ideal choice for large-scale energy storage. An aqueous battery refers to a secondary battery using water as an electrolyte solvent. Compared with an organic electrolyte battery, the water-based battery has the advantages of high safety, environmental friendliness, high ionic conductivity and the like, so that the water-based battery has a greater application prospect in future large-scale electric energy storage. At present, water-based batteries are mainly limited by the defects of narrow window voltage, serious electrode side reaction, poor cycle stability and the like, and in order to overcome the bottlenecks, researchers have developed water-based mixed metal batteries and single metal batteries (lithium, sodium, potassium, zinc batteries and the like) and have conducted a great deal of research on positive and negative electrode materials, electrolytes and energy storage mechanisms of the water-based mixed metal batteries and the single metal batteries.
Unlike organic electrolytes, aqueous electrolytes have a narrow stable potential window, and water decomposition must be carefully considered when selecting an electrode active material for a lithium ion water battery. In principle, e.g. LiCoO2、LiMn2O4、LiNixCo1-xO2、LiFePO4The reaction potential of the material is before the water decomposition potential, and thus the material can be used as a positive electrode material of a lithium ion water-based battery. Theoretically, a low potential negative electrode for receiving lithium ions and a high potential positive electrode for supplying lithium ions can be combined into a water-based lithium ion battery in a voltage range in which water is decomposed to separate hydrogen and oxygen.
In 1994, the first aqueous lithium ion battery was reported, which uses VO separately2And LiMn2O4As the negative electrode and the positive electrode, respectively, 5M LiNO was used3Is an electrolyte. However, the electrochemical window of the water-based lithium ion battery is narrow, so that the further large-scale application of the water-based lithium ion battery is restricted, and aiming at the problem, a novel salt-in-water electrolyte is adopted in recent years, so that the electrochemical window of the water-based lithium ion battery can reach 3.0V (1.9-4.9V vs. Li)+/Li) which is sufficiently comparable to that of an organic electrolyte and uses LiTFSI as a lithium salt, TFSI is a positive electrode for polarization-The film is reduced before water molecules to form a layer of SEI film similar to that in an organic electrolyte system, which is beneficial to improving the open-circuit voltage and the electrochemical performance of the battery.
Disclosure of Invention
The first purpose of the invention is to provide an aqueous lithium ion battery electrolyte based on oligomer, which has the characteristics of high voltage window and good cycle stability and is suitable for a high-pressure water-based lithium ion battery.
The second purpose of the invention is to provide application of the aqueous lithium ion battery electrolyte based on oligomer in an electrochemical energy storage device.
A third object of the present invention is to provide an electrochemical energy storage device.
In order to achieve the first purpose, the invention adopts the following technical scheme:
an oligomer-based aqueous lithium ion battery electrolyte solution comprising an oligomer solute, an electrolyte and water; wherein the content of the first and second substances,
the oligomer solute is selected from oligomers of pyrrole, aniline or thiophene;
the electrolyte is a lithium-containing soluble salt.
According to the research of the invention, the selected oligomer solute is preferentially adsorbed on the surface of the electrode, when free water molecules in the electrolyte contact the surface of the electrode, the electrode material and the oligomer solute preferentially undergo electron gain and loss reaction, and water is not decomposed until the voltage is higher or lower. In addition, the heteroatoms in the oligomer and free water molecules generate hydrogen bond interaction, so that the preferential reaction characteristic of the water molecules on the surface of the electrode can be overcome. By combining the two functions, the electrochemical stability window of the electrolyte is widened. On the other hand, the oligomer solute coats the electrode material in situ, so that the damage of the crystal structure of the material is avoided, the surface side reaction is inhibited, and the electronic conductivity and the ion transmission performance of the material are improved.
Further, the oligomer solute has a degree of polymerization of 2 to 10.
Further, the oligomer solute is obtained by adding pyrrole, aniline or thiophene monomers into an aqueous solution containing an oxidant, reacting, and centrifuging the supernatant. The voltage window under the condition is higher, and the cycling stability is better.
Further, the oxidant is selected from one or more of ferric chloride and ammonium persulfate.
Further, the concentration of the oxidizing agent in the aqueous solution of the oxidizing agent is 0.0005 to 0.005M. Illustratively, the concentration of the oxidizing agent includes, but is not limited to, 0.005M, 0.001-0.005M, 0.0005-0.001M, and the like.
Further, the concentration of the electrolyte in the electrolyte solution is 1-21M. Illustratively, the concentration of the electrolyte includes, but is not limited to, 10-21M, 10M, 21M, and the like.
Further, the concentration of the oligomer solute is 10-61M. Illustratively, the concentration of the oligomer solute includes, but is not limited to, 10-6M、10-3M, 1M, etc.
Further, the lithium-containing soluble salt is selected from one of lithium sulfate, lithium nitrate, lithium acetate, lithium bistrifluoromethanesulfonylimide and lithium bistrifluoromethanesulfonylimide.
To achieve the second object, the present invention provides the use of an electrolyte as described in the first object above in an electrochemical energy storage device.
To achieve the third object, the present invention provides an electrochemical energy storage device comprising the electrolyte as described in the first object.
Further, the electrochemical energy storage device is an aqueous secondary battery or an aqueous electrochemical supercapacitor or an organic combination of the two.
Further, the aqueous secondary battery is selected from aqueous lithium ion batteries.
Further, the aqueous lithium ion battery includes a positive electrode and a negative electrode; wherein the anode material is selected from lithium manganate, lithium iron phosphate or ternary material NCM 523; the negative electrode material is selected from titanium dioxide or lithium titanate.
The invention has the following beneficial effects:
the electrolyte provided by the invention is an aqueous electrolyte, has a high voltage window and is suitable for high-voltage aqueous lithium ion batteries. In the application and the electrochemical energy storage device provided by the invention, the electrolyte is adopted, so that the decomposition voltage of the electrolyte is improved, the working temperature is widened, the performance and the application range of the lithium ion battery are further improved, and a foundation is laid for the popularization and the application of the electrochemical energy storage device.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows the cycle performance test results obtained when the prepared aqueous electrolyte was used in an aqueous lithium ion battery in example 1.
Fig. 2 shows the results of testing the electrochemically stable voltage window obtained when the prepared aqueous electrolyte was used in an aqueous lithium ion battery in example 2.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
The aqueous electrolyte of the embodiment specifically comprises a solvent oligomer solution, and the electrolyte is lithium bistrifluoromethanesulfonylimide, and the preparation method comprises the following steps: FeCl at a concentration of 0.0005M in 10mL3Adding 1mL of pyrrole into the aqueous solution, taking a relatively clear supernatant after reaction, centrifuging, mixing the obtained clear oligomer solution with water to obtain a solution with the oligomer concentration of 10-3M, the aqueous electrolyte solution of this example was obtained by dissolving lithium bis (fluorosulfonyl) imide in the oligomer solution to prepare an electrolyte solution having an electrolyte concentration of 21M. The electrochemical window of the aqueous electrolyte prepared in this example was tested by three-electrode linear voltammetry, and the electrochemical stability window of the aqueous electrolyte reached 3.2V.
The aqueous electrolyte of the embodiment is used in an aqueous lithium ion battery, the anode is lithium manganate, the cathode is titanium dioxide, the anode and the cathode are mixed according to the weight ratio of active material/carbon black/PVDF (8/1/1) to prepare slurry, the anode material is coated on titanium foil, the cathode material is coated on carbon-coated aluminum foil, and the electrode is prepared after drying. And then assembling the lithium ion battery, wherein the used diaphragm is a glass fiber GFF diaphragm, and the electrolyte is the aqueous electrolyte of the embodiment. The charge and discharge test is carried out at 0.8-2.5V, the current density is 1A/g, the capacity retention rate is 94 percent after 3000 times of circulation at room temperature.
Example 2
The aqueous electrolyte of this example was specifically composed of a solvent oligomer solution and the electrolyte was a bis-polymerThe preparation method of the lithium trifluoromethanesulfonylimide comprises the following steps: FeCl at a concentration of 0.005M in 10mL3Adding 1mL of pyrrole into the aqueous solution, taking a relatively clear supernatant after reaction, centrifuging, mixing the obtained clear oligomer solution with water to obtain a solution with the oligomer concentration of 10-3M, the aqueous electrolyte solution of this example was obtained by dissolving lithium bis (fluorosulfonyl) imide in the oligomer solution to prepare an electrolyte solution having an electrolyte concentration of 21M. The electrochemical window of the aqueous electrolyte prepared in this example was tested by three-electrode linear voltammetry, and the electrochemical stability window of the aqueous electrolyte reached 3.2V.
The aqueous electrolyte of the embodiment is used in an aqueous lithium ion battery, the anode is lithium manganate, the cathode is titanium dioxide, the anode and the cathode are mixed according to the weight ratio of active material/carbon black/PVDF (8/1/1) to prepare slurry, the anode material is coated on titanium foil, the cathode material is coated on carbon-coated aluminum foil, and the electrode is prepared after drying. And then assembling the lithium ion battery, wherein the used diaphragm is a glass fiber GFF diaphragm, and the electrolyte is the aqueous electrolyte of the embodiment. The charge and discharge test is carried out at 0.8-2.5V, the current density is 1A/g, the capacity retention rate is 91 percent after 3000 times of circulation at room temperature.
Example 3
The aqueous electrolyte of the embodiment specifically comprises a solvent oligomer solution, and the electrolyte is lithium bistrifluoromethanesulfonylimide, and the preparation method comprises the following steps: FeCl at a concentration of 0.0005M in 10mL3Adding 1mL of pyrrole into the aqueous solution, taking a relatively clear supernatant after reaction, centrifuging, mixing the obtained clear oligomer solution with water to obtain a solution with the oligomer concentration of 10-3M, the aqueous electrolyte solution of this example was obtained by dissolving lithium bis (fluorosulfonyl) imide in the oligomer solution to prepare an electrolyte solution having an electrolyte concentration of 21M. The electrochemical window of the aqueous electrolyte prepared in this example was tested by three-electrode linear voltammetry, and the electrochemical stability window of the aqueous electrolyte reached 3.2V.
The aqueous electrolyte is used in an aqueous lithium ion battery, the positive electrode is lithium manganate, the negative electrode is lithium titanate, the positive electrode and the negative electrode are mixed according to the weight ratio of active material/carbon black/PVDF (polyvinylidene fluoride) of 8/1/1 to prepare slurry, the positive electrode material is coated on titanium foil, the negative electrode material is coated on aluminum foil, and the electrode is prepared after drying. And then assembling the lithium ion battery, wherein the used diaphragm is a glass fiber GFF diaphragm, and the electrolyte is the aqueous electrolyte of the embodiment. The charge and discharge test is carried out under the voltage of 1.5-2.8V, the current density is 1A/g, the capacity retention rate is 93 percent after 3000 times of circulation at room temperature.
Example 4
The aqueous electrolyte of the embodiment specifically comprises a solvent oligomer solution, and the electrolyte is lithium bistrifluoromethanesulfonylimide, and the preparation method comprises the following steps: FeCl at a concentration of 0.0005M in 10mL3Adding 1mL of pyrrole into the aqueous solution, taking a clear supernatant after reaction, centrifuging, mixing the obtained clear oligomer solution with water, and obtaining a solution with the oligomer concentration of 10-3M, the aqueous electrolyte solution of this example was obtained by dissolving lithium bis (fluorosulfonyl) imide in the oligomer solution to prepare an electrolyte solution having an electrolyte concentration of 21M. The electrochemical window of the aqueous electrolyte prepared in this example was tested by three-electrode linear voltammetry, and the electrochemical stability window of the aqueous electrolyte reached 3.2V.
The aqueous electrolyte of the embodiment is used in an aqueous lithium ion battery, the anode is lithium iron phosphate, the cathode is titanium dioxide, the anode and the cathode are mixed according to the weight ratio of active material/carbon black/PVDF (polyvinylidene fluoride) of 8/1/1 to prepare slurry, the anode material is coated on titanium foil, the cathode material is coated on carbon-coated aluminum foil, and the electrode is prepared after drying. And then assembling the lithium ion battery, wherein the used diaphragm is a glass fiber GFF diaphragm, and the electrolyte is the aqueous electrolyte of the embodiment. The charge and discharge test is carried out under 1-2.1V, the current density is 1A/g, the capacity retention rate is 95 percent after 4000 cycles at room temperature.
Example 5
The aqueous electrolyte of the embodiment specifically comprises a solvent oligomer solution, and the electrolyte is lithium bistrifluoromethanesulfonylimide, and the preparation method comprises the following steps: FeCl at a concentration of 0.0005M in 10mL3Adding 1mL of pyrrole into the aqueous solution, taking a clear supernatant after reaction, centrifuging, mixing the obtained clear oligomer solution with water, and obtaining a solution with the oligomer concentration of 10-3M, dissolving lithium bis (fluorosulfonyl) imide in the oligomer solution,an aqueous electrolyte solution of this example was obtained by preparing an electrolyte solution having an electrolyte concentration of 21M. The electrochemical window of the aqueous electrolyte prepared in this example was tested by three-electrode linear voltammetry, and the electrochemical stability window of the aqueous electrolyte reached 3.2V.
The aqueous electrolyte of the embodiment is used in an aqueous lithium ion battery, the anode is lithium iron phosphate, the cathode is lithium titanate, the anode and the cathode are mixed according to the weight ratio of active material/carbon black/PVDF (polyvinylidene fluoride) of 8/1/1 to prepare slurry, the anode material is coated on a titanium foil, the cathode material is coated on an aluminum foil, and the electrode is prepared after drying. And then assembling the lithium ion battery, wherein the used diaphragm is a glass fiber GFF diaphragm, and the electrolyte is the aqueous electrolyte of the embodiment. The charge and discharge test is carried out under 1-2.1V, the current density is 1A/g, the capacity retention rate is 94 percent after 4000 cycles at room temperature.
Example 6
The aqueous electrolyte of the embodiment specifically comprises a solvent oligomer solution, and the electrolyte is lithium bistrifluoromethanesulfonylimide, and the preparation method comprises the following steps: FeCl at a concentration of 0.0005M in 10mL3Adding 1mL of pyrrole into the aqueous solution, taking a relatively clear supernatant after reaction, centrifuging, mixing the obtained clear oligomer solution with water to obtain a solution with the oligomer concentration of 10-3M, the aqueous electrolyte solution of this example was obtained by dissolving lithium bis (fluorosulfonyl) imide in the oligomer solution to prepare an electrolyte solution having an electrolyte concentration of 21M. The electrochemical window of the aqueous electrolyte prepared in this example was tested by three-electrode linear voltammetry, and the electrochemical stability window of the aqueous electrolyte reached 3.2V.
The aqueous electrolyte is used in an aqueous lithium ion battery, the anode is a ternary material NCM523, the cathode is titanium dioxide, the anode and the cathode are mixed according to the weight ratio of active material/carbon black/PVDF (8/1/1) to prepare slurry, the anode material is coated on a titanium foil, the cathode material is coated on an aluminum foil, and the electrode is prepared after drying. And then assembling the lithium ion battery, wherein the used diaphragm is a glass fiber GFF diaphragm, and the electrolyte is the aqueous electrolyte of the embodiment. The charge and discharge test is carried out under 1-2.2V, the current density is 1A/g, the capacity retention rate is 92 percent after 3000 times of circulation at room temperature.
Example 7
The aqueous electrolyte of the embodiment specifically comprises a solvent oligomer solution, and the electrolyte is lithium bistrifluoromethanesulfonylimide, and the preparation method comprises the following steps: FeCl at a concentration of 0.0005M in 10mL3Adding 1mL of pyrrole into the aqueous solution, taking a relatively clear supernatant after reaction, centrifuging, mixing the obtained clear oligomer solution with water to obtain a solution with the oligomer concentration of 10-3M, the aqueous electrolyte solution of this example was obtained by dissolving lithium bis (fluorosulfonyl) imide in the oligomer solution to prepare an electrolyte solution having an electrolyte concentration of 21M. The electrochemical window of the aqueous electrolyte prepared in this example was tested by three-electrode linear voltammetry, and the electrochemical stability window of the aqueous electrolyte reached 3.2V.
The aqueous electrolyte is used in an aqueous lithium ion battery, the anode is a ternary material NCM523, the cathode is lithium titanate, the anode and the cathode are mixed according to the weight ratio of active material/carbon black/PVDF (polyvinylidene fluoride) 8/1/1 to prepare slurry, the anode material is coated on a titanium foil, the cathode material is coated on an aluminum foil, and the electrode is prepared after drying. And then assembling the lithium ion battery, wherein the used diaphragm is a glass fiber GFF diaphragm, and the electrolyte is the aqueous electrolyte of the embodiment. The charge and discharge test is carried out under 1.5-2.6V, the current density is 1A/g, the capacity retention rate is 90 percent after 3000 times of circulation at room temperature.
Example 8
Example 4 was repeated except that the aqueous electrolyte was changed to lithium bis (fluorosulfonylimide), the concentration of the electrolyte in the electrolyte solution was 10M, and the remaining conditions were not changed, so that the electrochemical stability window of the obtained aqueous electrolyte solution reached 3V.
The aqueous electrolyte was used in an aqueous lithium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0.8 to 2.5V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 92% after 2000 cycles at room temperature.
Example 9
Example 4 was repeated except that the oxidizing agent in the oligomer solute was changed to 0.0005M (NH)4)2S2O8And the rest conditions are unchanged, and the electrochemical stability window of the obtained water system electrolyte reaches 3.2V.
The aqueous electrolyte is used in an aqueous lithium ion battery according to the method of example 1, and a charge-discharge test is carried out at 1-2.5V, wherein the current density is 1A/g, and the capacity retention rate is 93% after the aqueous electrolyte is cycled for 4000 times at room temperature.
Example 10
Example 4 was repeated, except that the oligomer solute to water weight ratio was 2:1, and the remaining conditions were unchanged, and the electrochemical stability window of the obtained aqueous electrolyte reached 3.2V.
The aqueous electrolyte was used in an aqueous lithium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0.8 to 2.6V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 92% when it was cycled 3000 times at room temperature.
Example 11
Example 5 was repeated except that the aqueous electrolyte was changed to lithium bis (fluorosulfonylimide), the electrolyte concentration was 10M, and the remaining conditions were not changed, and the electrochemical stability window of the obtained aqueous electrolyte reached 3V.
The aqueous electrolyte was used in an aqueous lithium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0.8 to 2.5V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 91% when cycled 3000 times at room temperature.
Example 12
Example 5 was repeated except that the oxidizing agent in the oligomer solute was changed to 0.0005M (NH)4)2S2O8And the rest conditions are unchanged, and the electrochemical stability window of the obtained water system electrolyte reaches 3.2V.
The aqueous electrolyte was used in an aqueous lithium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 1.5 to 2.8V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 92% when cycled 3000 times at room temperature.
Example 13
Example 5 was repeated except that the oligomer solute to water weight ratio was 2:1, and the remaining conditions were unchanged, and the electrochemical stability window of the obtained aqueous electrolyte reached 3.2V.
The aqueous electrolyte was used in an aqueous lithium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0.8 to 2.6V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 93% when cycled 3000 times at room temperature.
Example 14
The aqueous electrolyte of the embodiment specifically comprises a solvent oligomer solution, and the electrolyte is lithium bistrifluoromethanesulfonylimide, and the preparation method comprises the following steps: FeCl at a concentration of 0.0005M in 10mL3Adding 1mL of aniline into the aqueous solution, centrifuging a relatively clear supernatant after reaction, mixing the obtained clear oligomer solution with water to obtain a solution with the oligomer concentration of 10-3M, the aqueous electrolyte solution of this example was obtained by dissolving lithium bis (fluorosulfonyl) imide in the oligomer solution to prepare an electrolyte solution having an electrolyte concentration of 21M. The electrochemical window of the aqueous electrolyte prepared in this example was tested by three-electrode linear voltammetry, and the electrochemical stability window of the aqueous electrolyte reached 3.0V.
The aqueous electrolyte of the embodiment is used in an aqueous lithium ion battery, the anode is lithium manganate, the cathode is titanium dioxide, the anode and the cathode are mixed according to the weight ratio of active material/carbon black/PVDF (8/1/1) to prepare slurry, the anode material is coated on titanium foil, the cathode material is coated on carbon-coated aluminum foil, and the electrode is prepared after drying. And then assembling the lithium ion battery, wherein the used diaphragm is a glass fiber GFF diaphragm, and the electrolyte is the aqueous electrolyte of the embodiment. The charge and discharge test is carried out at 0.8-2.5V, the current density is 1A/g, the capacity retention rate is 93 percent after 3000 times of circulation at room temperature.
Example 15
Example 3 was repeated, except that the conditions were not changed, and the pyrrole was changed to aniline, and the electrochemical stability window of the obtained aqueous electrolyte reached 3.1V.
The aqueous electrolyte was used in an aqueous lithium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 1.5 to 2.7V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 92% when cycled 3000 times at room temperature.
Example 16
Example 4 was repeated, except that the conditions were not changed, and the pyrrole was changed to aniline, and the electrochemical stability window of the obtained aqueous electrolyte reached 3.1V.
The aqueous electrolyte is used in an aqueous lithium ion battery according to the method of example 1, and a charge and discharge test is carried out at 0.5-2.0V, the current density is 1A/g, and the capacity retention rate is 95.5 percent after the aqueous electrolyte is cycled for 4000 times at room temperature.
Example 17
Example 1 was repeated, except that the conditions were not changed, and the electrochemical stability window of the obtained aqueous electrolyte reached 3.0V, in which pyrrole was replaced with thiophene.
The aqueous electrolyte was used in an aqueous lithium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0.7 to 2.6V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 92% when it was cycled 3000 times at room temperature.
Example 18
Example 3 was repeated, except that the conditions were not changed, and the electrochemical stability window of the obtained aqueous electrolyte reached 3.1V, in which pyrrole was replaced by thiophene.
The aqueous electrolyte was used in an aqueous lithium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 1.5 to 2.6V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 92% when cycled 3000 times at room temperature.
Example 19
Example 4 was repeated, except that the conditions were not changed, and the electrochemical stability window of the obtained aqueous electrolyte reached 3.0V, in which pyrrole was replaced with thiophene.
The aqueous electrolyte was used in an aqueous lithium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0.4 to 2.1V, with a current density of 1A/g, and a capacity retention rate of 93% after 4000 cycles at room temperature.
Comparative example 1
Example 17 was repeated, except that the "thiophene oligomer" obtained was changed to "diethyl sulfate", and the remaining conditions were not changed, to prepare an aqueous electrolyte solution having an electrochemical stability window of 2.5V.
The aqueous electrolyte was used in an aqueous lithium ion battery in accordance with the method of example 1, and a charge/discharge test was performed at 0.7 to 2.6V, and the aqueous electrolyte had a current density of 1A/g and a capacity retention rate of 15% after 3000 cycles at room temperature.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. An oligomer-based aqueous lithium ion battery electrolyte comprising an oligomer solute, an electrolyte and water; wherein the content of the first and second substances,
the oligomer solute is selected from oligomers of pyrrole, aniline or thiophene;
the electrolyte is a lithium-containing soluble salt.
2. The electrolyte of claim 1, wherein the oligomer solute has a degree of polymerization of 2 to 10;
preferably, the oligomer solute is obtained by adding pyrrole, aniline or thiophene monomer into an aqueous solution containing an oxidant, reacting, and centrifuging supernatant;
preferably, the oxidant is selected from one or more of ferric chloride and ammonium persulfate;
preferably, the concentration of the oxidizing agent in the aqueous solution of the oxidizing agent is 0.0005 to 0.005M.
3. The electrolyte of claim 1, wherein the concentration of the electrolyte in the electrolyte is 1-21M.
4. The electrolyte of claim 1, wherein the oligomer solute has a concentration of 10-6～1M。
5. The electrolyte of claim 1, wherein the lithium-containing soluble salt is selected from one of lithium sulfate, lithium nitrate, lithium acetate, lithium bistrifluoromethanesulfonylimide, and lithium bistrifluoromethanesulfonylimide.
6. Use of an electrolyte according to any of claims 1 to 5 in an electrochemical energy storage device.
7. An electrochemical energy storage device comprising an electrolyte as claimed in any one of claims 1 to 5.
8. An electrochemical energy storage device as in claim 7, wherein said electrochemical energy storage device is an aqueous secondary battery or an aqueous electrochemical supercapacitor or an organic combination of both.
9. An electrochemical energy storage device as in claim 8, wherein said water-based secondary battery is selected from water-based lithium ion batteries.
10. An electrochemical energy storage device as in claim 9, wherein said aqueous lithium ion battery comprises a positive electrode and a negative electrode; wherein the anode material is selected from lithium manganate, lithium iron phosphate or ternary material NCM 523; the negative electrode material is selected from titanium dioxide or lithium titanate.
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