CN117855634B - Electrolyte for improving energy density of lithium-zinc battery and preparation method thereof - Google Patents
Electrolyte for improving energy density of lithium-zinc battery and preparation method thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 88
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 33
- 239000000654 additive Substances 0.000 claims abstract description 51
- 230000000996 additive effect Effects 0.000 claims abstract description 51
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001868 water Inorganic materials 0.000 claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 31
- 239000011701 zinc Substances 0.000 claims abstract description 31
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 150000003751 zinc Chemical class 0.000 claims abstract description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910015645 LiMn Inorganic materials 0.000 claims description 12
- 229910052596 spinel Inorganic materials 0.000 claims description 12
- 239000011029 spinel Substances 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 9
- 229960001763 zinc sulfate Drugs 0.000 claims description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 16
- 238000001556 precipitation Methods 0.000 abstract description 9
- 239000002002 slurry Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 239000011268 mixed slurry Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 210000001787 dendrite Anatomy 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The electrolyte for improving the energy density of the lithium-zinc battery and the preparation method thereof provided by the application comprise water-soluble lithium salt, water-soluble zinc salt and additive compound, wherein the additive compound is a mixture comprising dimethyl diallyl ammonium chloride, polymer I and dodecyl trimethyl ammonium chloride, and the prepared electrolyte is used in a water-based lithium-zinc electrolyte by purposefully adjusting the adding proportion of each raw material in the additive compound, so that the precipitation of negative pole dendritic zinc can be effectively inhibited, the service life of the battery is ensured, and meanwhile, the lithium-zinc battery shows higher energy density, and the preparation method is low in cost and simple and is convenient to popularize and apply.
Description
Technical Field
The invention relates to the field of preparation of lithium-zinc battery electrolytes, in particular to an electrolyte for improving the energy density of a lithium-zinc battery and a preparation method thereof.
Background
At present, social development faces two significant problems of energy and environment, and with the massive use of underground resources and the increasing deterioration of the environment, the development of renewable energy has become a global trend. Among them, the battery has the advantage of high energy storage efficiency and is widely applied to the fields of automobiles, communication and the like. With the continuous enhancement of people's awareness of resource protection and environmental protection, the development of green and environment-friendly secondary batteries with high specific energy has become the mainstream.
The secondary battery mainly uses an anhydrous organic solution as electrolyte, ions can be reversibly deintercalated in an active material of a positive electrode and a negative electrode, and energy conversion is realized, wherein the development is a lithium ion battery. However, the electrolyte is prepared in an anhydrous environment, the environment requirement is severe, the production cost is high, the organic solvent in the electrolyte is toxic and flammable, the safety of the battery in the use process is low, and the development of the lithium battery in the energy storage field under the special environment is limited. The aqueous battery system has higher safety than organic electrolyte in the use process. China has rich metal zinc resources, low toxicity and low cost, so the research of a water system lithium zinc battery system attracts more and more attention.
However, in the long-term charge and discharge process of the water-based lithium-zinc battery, along with repeated dissolution and deposition of zinc on one side of a negative electrode, a phenomenon of zinc deposition in a dendrite state is easy to occur, and a diaphragm is seriously pierced, so that the battery is in short circuit failure; and the water system lithium zinc battery in the prior art has the problem of low energy density. In recent years, with the rapid development of new energy automobiles, the requirements of people on the endurance mileage and the battery life of the new energy automobiles are higher and higher, and the endurance total mileage of the electric automobiles is directly related to the energy density and the cycle stability of the power batteries carried by the electric automobiles.
Therefore, the research of the lithium zinc battery electrolyte which can improve the energy density of the battery and inhibit the precipitation of the dendritic zinc has great significance.
Disclosure of Invention
The invention aims at: aiming at the problems that the energy density of the water-based lithium-zinc battery is low and the zinc precipitation of the dendrite state easily occurs to the negative electrode in the prior art, the electrolyte for improving the energy density of the lithium-zinc battery and the preparation method thereof are provided, the electrolyte comprises water-soluble lithium salt, water-soluble zinc salt and an additive compound, wherein the additive compound is a mixture comprising dimethyl diallyl ammonium chloride, polymer I and dodecyl trimethyl ammonium chloride, and the prepared electrolyte is used in the water-based lithium-zinc electrolyte by purposefully adjusting the adding proportion of each raw material in the additive compound, so that the precipitation of the dendrite zinc of the negative electrode can be effectively inhibited, the service life of the battery is ensured, and meanwhile, the lithium-zinc battery shows higher energy density.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
An electrolyte for improving the energy density of a lithium-zinc battery comprises water-soluble lithium salt, water-soluble zinc salt and additive compound, wherein the water-soluble lithium salt, the water-soluble zinc salt and the additive compound are obtained by mixing the following raw materials;
Wherein the additive complex is a mixture comprising dimethyldiallylammonium chloride, polymer I and dodecyltrimethylammonium chloride; wherein, the adding weight ratio of the dimethyl diallyl ammonium chloride to the polymer I to the dodecyl trimethyl ammonium chloride is 0.8-1.2: 0.8 to 1.2:0.3 to 0.6;
Wherein the polymer I is a copolymer of acrylamide and dimethyl diallyl ammonium chloride.
The electrolyte for improving the energy density of the lithium-zinc battery comprises water-soluble lithium salt, water-soluble zinc salt and an additive compound, wherein the additive compound is a mixture comprising dimethyl diallyl ammonium chloride, a polymer I and dodecyl trimethyl ammonium chloride, and the prepared electrolyte is used in a water-based lithium-zinc electrolyte by pertinently adjusting the adding proportion of each raw material in the additive compound, so that the precipitation of negative pole dendritic zinc can be effectively inhibited, the service life of the battery is ensured, and meanwhile, the lithium-zinc battery shows higher energy density.
The additive compound provided by the application comprises dimethyl diallyl ammonium chloride, a polymer I and dodecyl trimethyl ammonium chloride which are mixed, wherein the dimethyl diallyl ammonium chloride and the polymer I can provide double bonds and cationic groups, the dodecyl trimethyl ammonium chloride can form good compatibility with two raw materials, good leveling property and certain adhesiveness are formed in electrolyte, an electron and ion migration path can be provided, ion conduction resistance is reduced, power and energy density are provided, a buffer layer is formed on one side of a negative electrode, zinc is uniformly deposited, generation of dendrite zinc is inhibited, and excellent electrochemical performance can be realized by adding a small amount of the compound into a battery, and higher energy density is shown.
Further, in the additive compound, the adding weight ratio of the dimethyldiallylammonium chloride to the polymer I to the dodecyltrimethylammonium chloride is 1:1:0.3 to 0.6. Through a great deal of experimental researches by the inventor, the addition proportion of the three raw materials in the researched addition compound directly influences the electrochemical performance of the electrolyte, and the experimental researches show that the electrolyte can not show good electrochemical performance when being applied to a lithium-zinc battery because only one raw material is added or only two raw materials are added, even the proportion of the three raw materials is not suitable. More preferably, the additive composition comprises dimethyl diallyl ammonium chloride, polymer I and dodecyl trimethyl ammonium chloride in an additive weight ratio of 1:1:0.5.
Further, the polymer I is prepared by the following steps:
Step 1, uniformly mixing acrylamide, dimethyl diallyl ammonium chloride and ammonium persulfate, and adding water to stir and dissolve;
step 2, stirring the mixed solution obtained in the step 1 under the condition of nitrogen to perform polymerization reaction for 2-3 h;
and step 3, sequentially carrying out washing treatment, drying treatment and grinding treatment on the materials reacted in the step 2 to obtain the polymer I.
Further, in the step 1, the adding mass ratio of the acrylamide to the dimethyldiallylammonium chloride is 2-3: 1.
In the step 1, the addition mass of the ammonium persulfate is 0.3-0.5% of that of the dimethyl diallyl ammonium chloride.
Further, in the step 2, the polymerization reaction temperature is 70 to 85 ℃.
Further, the water-soluble lithium salt is at least one of lithium chloride, lithium hexafluorophosphate and lithium tetrafluoroborate.
Further, the water-soluble zinc salt is at least one of zinc sulfate and zinc chloride.
Another object of the present invention is to provide an electrolyte comprising the above electrolyte.
An electrolyte of a lithium-zinc battery comprises water and the electrolyte for improving the energy density of the lithium-zinc battery; wherein, in the electrolyte, the concentration of lithium ions is 2-4 mol/L, the concentration of zinc ions is 2-4 mol/L, and the mass concentration of the additive compound is 1-3 g/L.
The aqueous electrolyte for the lithium-zinc battery mainly comprises water, lithium salt, zinc salt and the additive compound provided by the application, and the energy density of the battery can be effectively improved by adding the additive compound when the aqueous electrolyte is used in the lithium-zinc battery, so that zinc is uniformly precipitated on a negative electrode, good electrochemical performance is shown, and unexpected technical effects are achieved.
Further, the method comprises the following steps of slowly adding the electrolyte into water, and uniformly stirring to obtain the electrolyte of the lithium-zinc battery.
It is another object of the present invention to provide a lithium zinc battery comprising the above electrolyte.
A lithium zinc battery comprises a positive electrode, a negative electrode and the electrolyte; the active material of the positive electrode plate is spinel LiMn 2O4, and the negative electrode is a metal zinc plate.
The application provides a lithium zinc battery, the active material of the positive electrode plate is spinel LiMn 2O4, the negative electrode is a metal zinc plate, the electrolyte provided by the application effectively inhibits the precipitation of the negative electrode dendritic zinc, the safety of the battery is effectively improved, and the battery shows effective energy density.
Further, the lithium zinc battery also comprises a diaphragm, wherein the diaphragm is made of glass fiber materials or polypropylene materials.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. The electrolyte for improving the energy density of the lithium-zinc battery comprises water-soluble lithium salt, water-soluble zinc salt and an additive compound, wherein the additive compound is a mixture comprising dimethyl diallyl ammonium chloride, a polymer I and dodecyl trimethyl ammonium chloride, and the prepared electrolyte is used in a water-based lithium-zinc electrolyte by pertinently adjusting the adding proportion of each raw material in the additive compound, so that the precipitation of negative pole dendritic zinc can be effectively inhibited, the service life of the battery is ensured, and meanwhile, the lithium-zinc battery shows higher energy density.
2. The additive compound provided by the application comprises dimethyl diallyl ammonium chloride, a polymer I and dodecyl trimethyl ammonium chloride which are mixed, wherein the dimethyl diallyl ammonium chloride and the polymer I can provide double bonds and cationic groups, the dodecyl trimethyl ammonium chloride can form good compatibility with two raw materials, good leveling property and certain adhesiveness are formed in electrolyte, an electron and ion migration path can be provided, ion conduction resistance is reduced, power and energy density are provided, a buffer layer is formed on one side of a negative electrode, zinc is uniformly deposited, generation of dendrite zinc is inhibited, and excellent electrochemical performance can be realized by adding a small amount of the compound into a battery, and higher energy density is shown.
3. The aqueous electrolyte for the lithium-zinc battery mainly comprises water, lithium salt, zinc salt and the additive compound provided by the application, and the energy density of the battery can be effectively improved by adding the additive compound, and can reach more than 340Wh/kg, so that zinc is uniformly precipitated on a negative electrode, good electrochemical performance is shown, and unexpected technical effects are achieved.
4. The application provides a lithium zinc battery, the active material of the positive electrode plate is spinel LiMn 2O4, the negative electrode is a metal zinc plate, the electrolyte provided by the application effectively inhibits the precipitation of the negative electrode dendritic zinc, the safety of the battery is effectively improved, and the battery shows effective energy density, has low cost and is convenient to popularize and apply.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
Preparation of Polymer I
Step 1, uniformly mixing acrylamide, dimethyl diallyl ammonium chloride and ammonium persulfate, and adding water to stir and dissolve; wherein, the adding mass ratio of the acrylamide to the dimethyl diallyl ammonium chloride is 2.5:1, the addition mass of ammonium persulfate is 0.3 percent of that of dimethyl diallyl ammonium chloride.
Step 2, stirring the mixed solution obtained in the step 1 under the condition of nitrogen to perform polymerization reaction, wherein the reaction temperature is 70 ℃, and the reaction is performed for 3 hours;
and step 3, sequentially carrying out washing treatment, drying treatment and grinding treatment on the materials reacted in the step 2 to obtain the polymer I.
An additive composite prepared by mixing dimethyl diallyl ammonium chloride, a polymer I and dodecyl trimethyl ammonium chloride; the adding weight ratio of the dimethyl diallyl ammonium chloride to the polymer I to the dodecyl trimethyl ammonium chloride is 1:1:0.5;
preparation of electrolyte
Slowly adding lithium hexafluorophosphate, zinc sulfate 2 and an additive compound into water, and uniformly stirring to obtain electrolyte; in the electrolyte, the concentration of lithium ions is 3mol/L, the concentration of zinc ions is 3mol/L, and the mass concentration of the additive compound is 2g/L.
Preparation of lithium zinc cell
Spinel LiMn 2O4, acetylene black and PVDF are mixed according to the mass ratio of 8:1:1, then adding the mixture into NMP, grinding to prepare slurry, wherein the solid content of the slurry is 50% in mass ratio, then uniformly coating the mixed slurry on titanium foil, drying and cutting to obtain the positive electrode plate.
A metal zinc sheet was used as a negative electrode sheet, and a glass fiber film was prepared.
And assembling the positive electrode plate, the negative electrode plate, the electrolyte and the diaphragm into a battery.
Example 2
Preparation of Polymer I
Step 1, uniformly mixing acrylamide, dimethyl diallyl ammonium chloride and ammonium persulfate, and adding water to stir and dissolve; wherein, the adding mass ratio of the acrylamide to the dimethyl diallyl ammonium chloride is 2:1, the addition mass of ammonium persulfate is 0.4 percent of that of dimethyl diallyl ammonium chloride.
Step 2, stirring the mixed solution obtained in the step 1 under the condition of nitrogen to perform polymerization reaction, wherein the reaction temperature is 85 ℃, and the reaction is performed for 2 hours;
and step 3, sequentially carrying out washing treatment, drying treatment and grinding treatment on the materials reacted in the step 2 to obtain the polymer I.
An additive composite prepared by mixing dimethyl diallyl ammonium chloride, a polymer I and dodecyl trimethyl ammonium chloride; the adding weight ratio of the dimethyl diallyl ammonium chloride to the polymer I to the dodecyl trimethyl ammonium chloride is 0.8:1.2:0.3;
preparation of electrolyte
Slowly adding lithium chloride, zinc chloride and an additive compound into water, and uniformly stirring to obtain an electrolyte; in the electrolyte, the concentration of lithium ions is 2mol/L, the concentration of zinc ions is 4mol/L, and the mass concentration of the additive compound is 1g/L.
Preparation of lithium zinc cell
Spinel LiMn 2O4, acetylene black and PVDF are mixed according to the mass ratio of 8:1:1, then adding the mixture into NMP, grinding to prepare slurry, wherein the solid content of the slurry is 50% in mass ratio, then uniformly coating the mixed slurry on titanium foil, drying and cutting to obtain the positive electrode plate.
A metal zinc sheet was used as a negative electrode sheet, and a glass fiber film was prepared.
And assembling the positive electrode plate, the negative electrode plate, the electrolyte and the diaphragm into a battery.
Example 3
Preparation of Polymer I
Step 1, uniformly mixing acrylamide, dimethyl diallyl ammonium chloride and ammonium persulfate, and adding water to stir and dissolve; wherein, the adding mass ratio of the acrylamide to the dimethyl diallyl ammonium chloride is 3:1, the addition mass of ammonium persulfate is 0.5 percent of that of dimethyl diallyl ammonium chloride.
Step 2, stirring the mixed solution obtained in the step 1 under the condition of nitrogen to perform polymerization reaction, wherein the reaction temperature is 75 ℃, and the reaction time is 2.5 hours;
and step 3, sequentially carrying out washing treatment, drying treatment and grinding treatment on the materials reacted in the step 2 to obtain the polymer I.
An additive composite prepared by mixing dimethyl diallyl ammonium chloride, a polymer I and dodecyl trimethyl ammonium chloride; the adding weight ratio of the dimethyl diallyl ammonium chloride to the polymer I to the dodecyl trimethyl ammonium chloride is 1.2:0.8:0.6;
preparation of electrolyte
Slowly adding lithium tetrafluoroborate, zinc sulfate and additive compound into water, and uniformly stirring to obtain electrolyte; in the electrolyte, the concentration of lithium ions is 4mol/L, the concentration of zinc ions is 2mol/L, and the mass concentration of the additive compound is 3g/L.
Preparation of lithium zinc cell
Spinel LiMn 2O4, acetylene black and PVDF are mixed according to the mass ratio of 8:1:1, then adding the mixture into NMP, grinding to prepare slurry, wherein the solid content of the slurry is 50% in mass ratio, then uniformly coating the mixed slurry on titanium foil, drying and cutting to obtain the positive electrode plate.
A metal zinc sheet was used as a negative electrode sheet, and a glass fiber film was prepared.
And assembling the positive electrode plate, the negative electrode plate, the electrolyte and the diaphragm into a battery.
Comparative example 1
Comparative example 1 the electrolyte type was changed as compared with example 1, and the additive composite was not added to specific comparative example 1.
Preparation of electrolyte
Slowly adding lithium hexafluorophosphate and zinc sulfate into water, and uniformly stirring to obtain an electrolyte; in the electrolyte, the concentration of lithium ions is 3mol/L, and the concentration of zinc ions is 3mol/L.
Preparation of lithium zinc cell
Spinel LiMn 2O4, acetylene black and PVDF are mixed according to the mass ratio of 8:1:1, then adding the mixture into NMP, grinding to prepare slurry, wherein the solid content of the slurry is 50% in mass ratio, then uniformly coating the mixed slurry on titanium foil, drying and cutting to obtain the positive electrode plate.
A metal zinc sheet was used as a negative electrode sheet, and a glass fiber film was prepared.
And assembling the positive electrode plate, the negative electrode plate, the electrolyte and the diaphragm into a battery.
Comparative example 2
Comparative example 2 compared to example 1, an additive composite was provided in which no polymer I was added, and the remainder was identical to example 1, and the specific preparation process was as follows:
An additive composite prepared by mixing dimethyl diallyl ammonium chloride and dodecyl trimethyl ammonium chloride; the adding weight ratio of the dimethyl diallyl ammonium chloride to the dodecyl trimethyl ammonium chloride is 1:0.5;
preparation of electrolyte
Slowly adding lithium hexafluorophosphate, zinc sulfate 2 and an additive compound into water, and uniformly stirring to obtain electrolyte; in the electrolyte, the concentration of lithium ions is 3mol/L, the concentration of zinc ions is 3mol/L, and the mass concentration of the additive compound is 2g/L.
Preparation of lithium zinc cell
Spinel LiMn 2O4, acetylene black and PVDF are mixed according to the mass ratio of 8:1:1, then adding the mixture into NMP, grinding to prepare slurry, wherein the solid content of the slurry is 50% in mass ratio, then uniformly coating the mixed slurry on titanium foil, drying and cutting to obtain the positive electrode plate.
A metal zinc sheet was used as a negative electrode sheet, and a glass fiber film was prepared.
And assembling the positive electrode plate, the negative electrode plate, the electrolyte and the diaphragm into a battery.
Comparative example 3
Comparative example 3 the procedure of example 1 was followed except that dimethyl diallyl ammonium chloride was not added to the compound, and the procedure was as in example 1, except that:
Preparation of Polymer I
Step 1, uniformly mixing acrylamide, dimethyl diallyl ammonium chloride and ammonium persulfate, and adding water to stir and dissolve; wherein, the adding mass ratio of the acrylamide to the dimethyl diallyl ammonium chloride is 2.5:1, the addition mass of ammonium persulfate is 0.3 percent of that of dimethyl diallyl ammonium chloride.
Step 2, stirring the mixed solution obtained in the step 1 under the condition of nitrogen to perform polymerization reaction, wherein the reaction temperature is 70 ℃, and the reaction is performed for 3 hours;
and step 3, sequentially carrying out washing treatment, drying treatment and grinding treatment on the materials reacted in the step 2 to obtain the polymer I.
An additive complex prepared by mixing polymer I and dodecyltrimethylammonium chloride; the weight ratio of the polymer I to the dodecyl trimethyl ammonium chloride is 1:0.5;
preparation of electrolyte
Slowly adding lithium hexafluorophosphate, zinc sulfate 2 and an additive compound into water, and uniformly stirring to obtain electrolyte; in the electrolyte, the concentration of lithium ions is 3mol/L, the concentration of zinc ions is 3mol/L, and the mass concentration of the additive compound is 2g/L.
Preparation of lithium zinc cell
Spinel LiMn 2O4, acetylene black and PVDF are mixed according to the mass ratio of 8:1:1, then adding the mixture into NMP, grinding to prepare slurry, wherein the solid content of the slurry is 50% in mass ratio, then uniformly coating the mixed slurry on titanium foil, drying and cutting to obtain the positive electrode plate.
A metal zinc sheet was used as a negative electrode sheet, and a glass fiber film was prepared.
And assembling the positive electrode plate, the negative electrode plate, the electrolyte and the diaphragm into a battery.
Comparative example 4
Comparative example 4 the preparation was carried out in the same manner as in example 1 except that dodecyltrimethylammonium chloride was not added to the compound, as compared with example 1, as follows:
Preparation of Polymer I
Step 1, uniformly mixing acrylamide, dimethyl diallyl ammonium chloride and ammonium persulfate, and adding water to stir and dissolve; wherein, the adding mass ratio of the acrylamide to the dimethyl diallyl ammonium chloride is 2.5:1, the addition mass of ammonium persulfate is 0.3 percent of that of dimethyl diallyl ammonium chloride.
Step 2, stirring the mixed solution obtained in the step 1 under the condition of nitrogen to perform polymerization reaction, wherein the reaction temperature is 70 ℃, and the reaction is performed for 3 hours;
and step 3, sequentially carrying out washing treatment, drying treatment and grinding treatment on the materials reacted in the step 2 to obtain the polymer I.
An additive compound prepared by mixing dimethyl diallyl ammonium chloride and a polymer I; the adding weight ratio of the dimethyl diallyl ammonium chloride to the polymer I is 1:1.
Preparation of electrolyte
Slowly adding lithium hexafluorophosphate, zinc sulfate 2 and an additive compound into water, and uniformly stirring to obtain electrolyte; in the electrolyte, the concentration of lithium ions is 3mol/L, the concentration of zinc ions is 3mol/L, and the mass concentration of the additive compound is 2g/L.
Preparation of lithium zinc cell
Spinel LiMn 2O4, acetylene black and PVDF are mixed according to the mass ratio of 8:1:1, then adding the mixture into NMP, grinding to prepare slurry, wherein the solid content of the slurry is 50% in mass ratio, then uniformly coating the mixed slurry on titanium foil, drying and cutting to obtain the positive electrode plate.
A metal zinc sheet was used as a negative electrode sheet, and a glass fiber film was prepared.
And assembling the positive electrode plate, the negative electrode plate, the electrolyte and the diaphragm into a battery, and performing electrochemical performance test.
Comparative example 5
Comparative example 5 the proportions of the three raw materials were changed in the addition of the compound compared to example 1, and the rest was the same as in example 1, and the specific preparation process was as follows:
Preparation of Polymer I
Step 1, uniformly mixing acrylamide, dimethyl diallyl ammonium chloride and ammonium persulfate, and adding water to stir and dissolve; wherein, the adding mass ratio of the acrylamide to the dimethyl diallyl ammonium chloride is 2.5:1, the addition mass of ammonium persulfate is 0.3 percent of that of dimethyl diallyl ammonium chloride.
Step 2, stirring the mixed solution obtained in the step 1 under the condition of nitrogen to perform polymerization reaction, wherein the reaction temperature is 70 ℃, and the reaction is performed for 3 hours;
and step 3, sequentially carrying out washing treatment, drying treatment and grinding treatment on the materials reacted in the step 2 to obtain the polymer I.
An additive composite prepared by mixing dimethyl diallyl ammonium chloride, a polymer I and dodecyl trimethyl ammonium chloride; the adding weight ratio of the dimethyl diallyl ammonium chloride to the polymer I to the dodecyl trimethyl ammonium chloride is 0.4:1:1, a step of;
preparation of electrolyte
Slowly adding lithium hexafluorophosphate, zinc sulfate 2 and an additive compound into water, and uniformly stirring to obtain electrolyte; in the electrolyte, the concentration of lithium ions is 3mol/L, the concentration of zinc ions is 3mol/L, and the mass concentration of the additive compound is 2g/L.
Preparation of lithium zinc cell
Spinel LiMn 2O4, acetylene black and PVDF are mixed according to the mass ratio of 8:1:1, then adding the mixture into NMP, grinding to prepare slurry, wherein the solid content of the slurry is 50% in mass ratio, then uniformly coating the mixed slurry on titanium foil, drying and cutting to obtain the positive electrode plate.
A metal zinc sheet was used as a negative electrode sheet, and a glass fiber film was prepared.
And assembling the positive electrode plate, the negative electrode plate, the electrolyte and the diaphragm into a battery.
Testing
The energy density and cycle performance of the lithium zinc batteries prepared in examples 1 to 3 and comparative examples 1 to 5 were measured, and the specific operation methods are shown below, and the specific test data are shown in table 1.
Detection of energy density
Under normal temperature, charging the lithium zinc battery to 2.1V according to constant current and constant voltage of 0.2C, and stopping current of 0.05C; then, the mixture is left for 10 minutes; then discharging to 0.8V according to the constant current of 0.5C, recording the discharge energy under the condition, dividing the discharge energy (Wh) by the battery mass (kg) to obtain the energy density (Wh/kg) of the battery;
Detection of circulation capacity
Under normal temperature, charging the lithium zinc battery to 2.1V according to constant current and constant voltage of 0.2C, and stopping current of 0.05C; then, the mixture is left for 10 minutes; then, the discharge was carried out at a constant current of 0.5C to 0.8V, the number of cycles when the capacity was reduced to 80% of the nominal capacity was recorded, and the state of zinc deposition on the negative electrode was observed.
Table 1 electrochemical performance test data for lithium zinc batteries
As shown by the test results of Table 1, the electrolytes provided in examples 1-3 are used in aqueous lithium-zinc electrolyte, can effectively inhibit the precipitation of negative pole dendritic zinc, ensure the service life of the battery, and simultaneously enable the lithium-zinc battery to show higher energy density, lower cost and simple preparation method. The comparative example proves that the electrolyte applied to the lithium zinc battery cannot show good electrochemical performance by only adding one raw material or only adding two raw materials, even if the ratio of the three raw materials is not proper, and the adding proportion of the three raw materials in the added compound is a key factor influencing the electrochemical performance of the electrolyte.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. An electrolyte of a lithium-zinc battery is characterized by comprising water and electrolyte; the electrolyte comprises a water-soluble lithium salt, a water-soluble zinc salt and an additive complex;
Wherein the additive complex is a mixture comprising dimethyldiallylammonium chloride, polymer I and dodecyltrimethylammonium chloride; wherein, the adding weight ratio of the dimethyl diallyl ammonium chloride to the polymer I to the dodecyl trimethyl ammonium chloride is 0.8-1.2: 0.8 to 1.2:0.3 to 0.6;
The polymer I is prepared by the following steps:
Step 1, uniformly mixing acrylamide, dimethyl diallyl ammonium chloride and ammonium persulfate, and adding water to stir and dissolve;
step 2, stirring the mixed solution obtained in the step 1 under the condition of nitrogen to perform polymerization reaction for 2-3 h;
step 3, subjecting the materials reacted in the step 2 to washing treatment, drying treatment and grinding treatment in sequence to obtain a polymer I;
wherein the polymer I is a copolymer of acrylamide and dimethyl diallyl ammonium chloride;
wherein, in the electrolyte, the concentration of lithium ions is 2-4 mol/L, the concentration of zinc ions is 2-4 mol/L, and the mass concentration of the additive compound is 1-3 g/L.
2. The electrolyte according to claim 1, wherein in the step 2, the polymerization reaction temperature is 70 to 85 ℃.
3. The electrolyte of claim 1, wherein the water-soluble lithium salt is at least one of lithium chloride, lithium hexafluorophosphate, and lithium tetrafluoroborate.
4. The electrolyte of claim 1 wherein the water soluble zinc salt is at least one of zinc sulfate and zinc chloride.
5. The method for preparing the electrolyte of the lithium-zinc battery according to claim 4, which is characterized by comprising the following steps of slowly adding the electrolyte into water and uniformly stirring to obtain the electrolyte of the lithium-zinc battery.
6. A lithium zinc battery comprising a positive electrode, a negative electrode and the electrolyte of claim 1; the active material of the positive electrode plate is spinel LiMn 2O4, and the negative electrode is a metal zinc plate.
7. The lithium zinc battery according to claim 6, further comprising a separator made of glass fiber or polypropylene.
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| JPS6217963A (en) * | 1985-07-15 | 1987-01-26 | Mitsui Toatsu Chem Inc | Storage battery |
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| JP2017171825A (en) * | 2016-03-25 | 2017-09-28 | 積水化成品工業株式会社 | Hydrogel and manufacturing method therefor |
| CN112259722A (en) * | 2020-10-28 | 2021-01-22 | 苏州大学 | Water system mixed ion secondary battery and preparation method and application thereof |
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