CN115425230A - Negative electrode modifier and preparation method and application thereof - Google Patents
Negative electrode modifier and preparation method and application thereof Download PDFInfo
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- CN115425230A CN115425230A CN202211374252.1A CN202211374252A CN115425230A CN 115425230 A CN115425230 A CN 115425230A CN 202211374252 A CN202211374252 A CN 202211374252A CN 115425230 A CN115425230 A CN 115425230A
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- 239000003607 modifier Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 68
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 241000219357 Cactaceae Species 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000004108 freeze drying Methods 0.000 claims abstract description 23
- 238000007710 freezing Methods 0.000 claims abstract description 20
- 230000008014 freezing Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims description 39
- 239000006258 conductive agent Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000006230 acetylene black Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000011883 electrode binding agent Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000011267 electrode slurry Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000003273 ketjen black Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 17
- 210000001787 dendrite Anatomy 0.000 description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 15
- 239000006256 anode slurry Substances 0.000 description 9
- 230000002441 reversible effect Effects 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- UDKXBPLHYDCWIG-UHFFFAOYSA-M [S-2].[S-2].[SH-].S.[V+5] Chemical compound [S-2].[S-2].[SH-].S.[V+5] UDKXBPLHYDCWIG-UHFFFAOYSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- 239000002135 nanosheet Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
-
- 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
- H01M2004/027—Negative 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
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a negative electrode modifier and a preparation method and application thereof. The preparation method comprises the following steps: and sequentially freezing, freeze-drying and grinding the pretreated cactus segments to obtain the negative electrode modifier. The invention simply processes common cactus in life to prepare the edible water system zinc ion battery cathode modifier, and carries out coating modification on the cathode zinc foil by a conventional battery pole piece coating mode. The negative electrode modifier disclosed by the invention is easy to obtain raw materials, simple in method, universal and suitable for the field of large-scale energy storage.
Description
Technical Field
The invention relates to the field of zinc ion batteries, relates to a preparation method of a negative electrode modifier, and particularly relates to a negative electrode modifier and a preparation method and application thereof.
Background
With the rapid increase of energy demand, many countries and regions have increased the investment in renewable energy sources such as solar energy, wind energy, and hydropower to cope with the global challenge of the increasing exhaustion of traditional fossil energy and the related environmental problems. Although low-carbon or non-carbon clean energy exists, the generation and conversion of a renewable energy power supply system have the characteristics of intermittence, instability, uncontrollable and the like. Non-aqueous lithium ion batteries are currently the most widely used rechargeable electrochemical devices. However, due to increasing concerns about their potential safety issues, large-scale application of lithium ion batteries is hampered. In addition, the high cost and low abundance of lithium resources on earth have also limited the long-term development of lithium ores. Compared with the traditional lithium battery based on organic electrolyte, the water system zinc ion battery has the characteristics of higher safety, lower cost, easier processing and higher ionic conductivity, and has the prospect of large-scale energy storage.
Zinc is naturally abundant, about 300 times as abundant as lithium, and has good resistance to the environment, so that it is low in purchase and processing costs. Very importantly, zn anodes also have the inherent advantage of high theoretical capacity. Therefore, water-based zinc ion batteries have attracted sufficient attention. It is known that the negative electrode is an important component of an aqueous zinc ion battery, and is particularly important for the performance and life of the battery. However, despite the inherent advantages of zinc cathodes, zn dendrite growth therein remains a challenge, a problem that can be devastating to aqueous zinc ion batteries. According to previous reports, dendrite growth significantly reduces the capacity and coulombic efficiency of zinc anodes. Moreover, the zinc dendrites can pierce through the membrane during the circulation process to cause short circuit in the battery, even cause safety problems, and greatly limit the further development and application of the zinc ion battery. According to the mechanism of inhibiting the growth of zinc dendrite in the prior art, an artificial interface layer is constructed on the surface of metal zinc to obtain a stable zinc metal surface with a protective film, so that the growth of the zinc dendrite is inhibited, the long circulation stability of a zinc ion battery can be improved, but most of the existing artificial interface layers are organic additives, and the problems of complex manufacturing process, organic toxicity and low stability exist.
CN 114835161A discloses a zinc ion battery cathode, a preparation method of an active material of the zinc ion battery cathode, and a zinc ion battery. The preparation method of the zinc ion battery cathode active material comprises the step of preparing a vanadium tetrasulfide cathode active material, and providing a large number of active sites for embedding and removing zinc ions. Thereby improving the migration kinetics of zinc ions, reducing the growth of zinc dendrites and further improving the sequential stability of the cathode material. However, the preparation method of vanadium tetrasulfide needs hydrothermal reaction of a vanadium source and a sulfur source, the consumption of the preparation process is large, and the application of the hydrothermal reaction in industry is difficult to realize large-scale production.
CN 114899349A discloses a method for inhibiting growth of zinc dendrite by zinc modification of a zinc ion battery negative electrode. PVB, absolute ethyl alcohol and Nafion solution are prepared according to a certain proportion, and an artificial interface layer is constructed on the zinc electrode sheet by a spin coating method. However, the preparation method is complex and is not suitable for large-scale production.
Therefore, the development of a simple, convenient and environmentally friendly feasible solution capable of inhibiting the growth of zinc dendrites is the key to the practical application of zinc ion batteries.
Disclosure of Invention
The invention aims to provide a negative electrode modifier and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a preparation method of a negative electrode modifier, which comprises the following steps: and sequentially freezing, freeze-drying and grinding the pretreated cactus segments to obtain the negative electrode modifier.
The negative electrode modifier disclosed by the invention is easy to obtain raw materials, simple in method, universal and suitable for the field of large-scale energy storage. Researches show that the technical scheme provided by the invention has the influence on the redeposition morphology of the zinc cathode and the formation of zinc dendrites on the basis of not influencing the advantages of the water-based zinc ion battery, and the corresponding zinc cathode surface can be deposited more uniformly. Under different current densities, considerable reversible specific capacity is shown, and the overall cycle and rate performance of the battery can be effectively enhanced.
The freeze-drying operation of the invention is premised on that the sample is in a complete freezing state, so the sample needs to be frozen before freeze-drying, and the sample is ensured to be in a complete freezing state without water. The freeze-drying treatment aims to directly sublimate the frozen and solidified liquid in the middle of the sample, so that the original components of the original sample are kept to the maximum extent, the structure of the sample is ensured not to collapse, the freeze-drying treatment completely freezes the moisture in pores of the cactus, and the moisture still exists in the cell structure of the microstructure in the cactus. Compared with common drying, the freeze-drying is carried out under the conditions of low temperature and low pressure, the water is not directly sublimated through liquid state, the composition of each component in the cactus sample can be maintained, and particularly, the volatile heat-sensitive components in the cactus sample are ensured not to be lost, so that the oxidation, the conversion of nutrient components and the change of state in the drying process are effectively prevented. As a preferred technical scheme of the invention, the pretreatment comprises the step of removing thorns on the surface of the cactus.
The spine includes long spine and villus, and the spine in the invention may include long spine or villus.
The cut length of the cactus segment is 3 to 6cm, wherein the cut length can be 3cm, 4 cm, 5cm or 6cm, and the like, but the cut length is not limited to the listed numerical value, and other numerical values which are not listed in the numerical value range are also applicable.
In a preferred embodiment of the present invention, the freezing temperature is-40 to-60 ℃, and the freezing temperature may be-40 ℃, -45 ℃, -50 ℃, -55 ℃, or-60 ℃, but the freezing temperature is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
The excessive temperature of the freezing treatment in the invention easily causes that the moisture in the sample can not be completely solidified in an effective time, thereby causing the problems of component loss or structure collapse of the cactus sample during the freeze-drying operation.
The freezing time is 6 to 24h, wherein the freezing time can be 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, and the like, but the freezing time is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
The freeze-drying time is 20 to 40h, wherein the freeze-drying time can be 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h or 40h, and the like, but the freeze-drying time is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
The freeze-drying time in the invention is too short, so that the solid water in the cactus sample can not be completely treated due to incomplete freeze-drying, and the freeze-dried structure is changed into the original liquid state due to temperature rise so as to collapse the sample structure.
The particle size of the negative electrode modifier is 60 to 90 [ mu ] m, wherein the particle size can be 60 [ mu ] m, 65 [ mu ] m, 70 [ mu ] m, 75 [ mu ] m, 80 [ mu ] m, 85 [ mu ] m or 90 [ mu ] m, and the like, but the particle size is not limited to the enumerated numerical values, and other numerical values not enumerated in the numerical value range are also applicable.
When the particle size of the negative electrode modifier is too long, the modified coating falls off easily in the circulation process due to the too large particle size, so that the circulation performance of the battery is influenced; when the particle size is too short, the smaller particle size may not fully function as a barrier against zinc dendrites, and the particle size herein refers to the particle size of all negative electrode modifiers.
The second object of the present invention is to provide a negative electrode modifier prepared by the method for preparing the negative electrode modifier according to the first object.
The negative electrode modifier comprises the following elements in parts by weight: 19.48wt% C, 0.72wt% N, 14.35wt% O, 0.35 wt% Mg, 0.74 wt% Al, 2.34wt% K, 0.08wt% Zn and 61.94wt% Au.
The negative electrode modifier has a tea-shaped lamellar structure, and due to the special spatial structure of the negative electrode modifier, the negative electrode modifier can fully play a role in protecting a zinc negative electrode through reasonable surface compounding: 1) The special layered structure enlarges the transmission channel of zinc ions, and provides guarantee for accelerated ion transmission; the soft and loose 'tea-shaped' structure establishes a natural physical interlayer between the zinc dendrite and the diaphragm, further prevents the problem of short circuit of the battery caused by the dendrite, and improves the sequential performance of the battery and the safety coefficient of the battery.
The invention also provides a negative plate, which is characterized by comprising a negative current collector and a negative active layer arranged on the negative current collector, wherein the negative active layer comprises a negative conductive agent, a negative binder and the second negative modifier.
As a preferred embodiment of the present invention, the negative electrode conductive agent includes any one of Super P, acetylene black, or ketjen black, or a combination of at least two thereof, wherein the combination is typically, but not limited to, exemplified by: a combination of Super P and acetylene black, a combination of acetylene black and ketjen black, a combination of Super P and ketjen black, or the like.
The negative electrode binder includes PVDF.
The mass ratio of the negative electrode modifier, the negative electrode conductive agent and the negative electrode binder is (6.5 to 7.5): 1.5, wherein the mass ratio can be: 1, etc., but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
The negative current collector includes a zinc foil.
The fourth object of the present invention is to provide an aqueous zinc-ion battery comprising the negative electrode sheet according to the third object.
A fifth object of the present invention is to provide a method for producing an aqueous zinc-ion battery according to the fourth object, the method comprising the steps of:
(1) Mixing a negative electrode modifier, a negative electrode conductive agent and a negative electrode binder in a solvent to obtain negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, drying and pressurizing to obtain a negative electrode sheet;
(2) And (3) assembling the positive plate and the negative plate in the step (1), a diaphragm and electrolyte to obtain the water-based zinc ion battery.
The invention simply processes common cactus in life to prepare the novel edible water system zinc ion battery negative electrode modifier, and carries out coating modification on the negative electrode current collector by a conventional battery pole piece coating mode, thereby playing the roles of protecting and modifying the negative electrode current collector.
The negative electrode in the invention is zinc foil.
According to the invention, a water-based zinc ion positive electrode active substance, a positive electrode conductive agent and a positive electrode binder are mixed in a positive electrode solvent to obtain a positive electrode slurry, the positive electrode slurry is coated on a positive electrode current collector, and a positive electrode sheet is obtained through drying and pressurization.
The aqueous zinc ion positive active material includes any one of α -manganese dioxide, δ -manganese dioxide, γ -manganese dioxide, or vanadium pentoxide, or a combination of at least two thereof, wherein typical but non-limiting examples of the combination are: a combination of α -manganese dioxide and δ -manganese dioxide, a combination of δ -manganese dioxide and γ -manganese dioxide, a combination of γ -manganese dioxide and vanadium pentoxide, or the like.
The positive electrode conductive agent includes any one of Super P, acetylene black or Ketjen black or a combination of at least two of the above, wherein the combination is typically but not limited to: a combination of Super P and acetylene black, a combination of acetylene black and ketjen black, a combination of Super P and ketjen black, or the like.
The positive electrode binder includes PVDF.
The mass ratio of the aqueous zinc ion positive electrode active material, the positive electrode conductive agent and the positive electrode binder is (6.5 to 7.5): 1, wherein the mass ratio can be 6.5: 1, etc., but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
As a preferred embodiment of the present invention, the solvent in step (1) comprises NMP.
The mixing in step (1) is carried out in a ball mill.
The mixing time in the step (1) is 25 to 35min, wherein the mixing time can be 25 min, 26 min, 27 min, 28 min, 29 min, 30 min, 31 min, 32 min, 33 min, 34 min or 35min, and the like, but the mixing time is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
The drying temperature in the step (1) is 55 to 65 ℃, wherein the temperature can be 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃ or 65 ℃, and the like, but the drying temperature is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
The pressurizing pressure in the step (1) is 5 to 15mpa, wherein the pressure may be 5Mpa, 6 Mpa, 7 Mpa, 8 Mpa, 9 Mpa, 10 Mpa, 11 Mpa, 12 Mpa, 13 Mpa, 14 Mpa or 15Mpa, but is not limited to the recited values, and other values not recited in the above range are also applicable.
As a preferable technical solution of the present invention, the separator in the step (2) includes a glass fiber separator.
The electrolyte comprises ZnSO 4 /MnSO 4 Solution or Zn (CF) 3 SO 3 ) 2 And (3) solution.
The ZnSO 4 /MnSO 4 ZnSO in solution 4 The concentration of the solution is 1 to 5mol/L, wherein the concentration can be 1 mol/L, 2 mol/L, 3mol/L, 4 mol/L or 5mol/L, but the concentration is not limited to the recited numerical values, and other numerical values not recited in the numerical value range are also applicable.
The ZnSO 4 /MnSO 4 MnSO in solution 4 The concentration of the solution is 0.1 to 0.5mol/L, wherein the concentration can be 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, 0.4 mol/L or 0.5mol/L, but the solution is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The Zn (CF) 3 SO 3 ) 2 The concentration of the solution is 1 to 3mol/L, wherein the concentration can be 1 mol/L, 2 mol/L or 3mol/L, but the concentration is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Compared with the prior art, the invention has the following beneficial effects:
the invention simply processes common cactus in life, prepares the novel edible aqueous zinc ion battery negative electrode modifier, and carries out coating modification on the negative electrode zinc foil by a conventional battery pole piece coating mode. The additive disclosed by the invention is easy to obtain raw materials, simple in method, universal and suitable for the field of large-scale energy storage. In addition, the technical scheme provided by the invention can effectively enhance the specific capacity and stability of the original active material on the basis of not influencing the advantages of the water-based zinc ion battery. Wherein, the high specific capacity of more than 294mAh/g, more than 246.3mAh/g, more than 183.1mAh/g, more than 137.2mAh/g and more than 88.9mAh/g can be respectively achieved under the current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g and 2A/g.
Drawings
Fig. 1 is a plot of cyclic voltammetry at different rates for a zinc ion cell of example 1 of the invention.
Fig. 2 is a charge-discharge curve diagram of the zinc ion battery in example 1 of the present invention at different rates.
Fig. 3 is a graph of the rate performance of the zinc-ion battery of example 1 of the present invention.
Fig. 4 is a sequential performance diagram of the zinc-ion battery in example 1 of the present invention.
Fig. 5 is an SEM image of the surface of the zinc negative electrode after 500 cycles of the constant current cycle test of the zinc ion battery in example 1 of the present invention at a current density of 1A/g.
FIG. 6 is a scanning electron micrograph of a negative electrode modifier in example 1 of the present invention.
Fig. 7 is a composition spectrum of elements in the negative electrode modifier in example 1 of the present invention.
Fig. 8 is a graph of rate performance of the zinc-ion battery in example 6 of the invention.
Fig. 9 is a graph of rate performance of a zinc-ion battery in example 7 of the invention.
Fig. 10 is a graph of rate performance of a zinc-ion battery in example 8 of the invention.
Fig. 11 is a graph of rate performance of a zinc-ion battery in example 9 of the invention.
Fig. 12 is a graph of rate performance of the zinc-ion battery of comparative example 1 of the present invention.
Fig. 13 is a sequential performance graph of the zinc-ion cell of comparative example 1 of the present invention.
Fig. 14 is an SEM image of the surface of the zinc negative electrode after 500 cycles of the constant current cycle test of the zinc-ion battery in comparative example 1 of the present invention at a current density of 1A/g.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a negative electrode modifier, which comprises the following steps:
cleaning long thorns and villi on the surface of the cactus, cutting off 5cm to obtain a cactus section after surface treatment, and sequentially freezing the cactus section after surface treatment at the temperature of 50 ℃ below zero for 20 hours, freeze-drying for 24 hours and grinding to obtain the negative electrode modifier.
The embodiment also provides a preparation method of the water-based zinc ion battery, and the water-based new ion battery comprises a negative plate, and the negative plate is obtained by the preparation method of the negative electrode modifier. Wherein. The preparation method of the water system zinc ion battery comprises the following steps:
(1) In a first solvent NMP, the following steps of (1) dissolving an aqueous zinc ion positive electrode active material alpha-manganese dioxide, a positive electrode conductive agent acetylene black and a positive electrode binder PVDF in a first solvent NMP according to a ratio of 7:2:1, mixing the materials by a ball mill to obtain anode slurry, coating the anode slurry on a titanium foil of an anode current collector, performing vacuum drying at 80 ℃ for 24 hours, removing a solvent, and finally punching the anode slurry into an anode sheet with the diameter of 12mm by a sheet cutter for later use; ball-milling and mixing a negative electrode modifier, a negative electrode conductive agent acetylene black and a negative electrode binder PVDF in a third NMP by using a ball mill to obtain a negative electrode slurry, coating the negative electrode slurry on a 0.05mm negative electrode current collector zinc foil, drying and pressurizing to obtain a negative electrode sheet;
(2) Mixing the positive plate and the negative plate in the step (1), the glass fiber diaphragm and electrolyte ZnSO 4 (2 mol/L)/MnSO 4 (0.2 mol/L) was assembled to obtain an aqueous zinc ion battery.
The cyclic voltammetry curves of the zinc ion battery prepared in the embodiment at different rates are shown in fig. 1, and it can be seen that the CV curves of the electrode at different sweep rates have smaller peak position shifts, indicating excellent reversibility and stability in electrochemical behavior. The charging and discharging curves with different multiplying factors in the embodiment are shown in fig. 2, and can beIt is clear that the discharge plateau for the cells is long and flat and is between 0.1-2A g -1 Is well maintained between the charging/discharging processes. The rate performance graph in this example is shown in fig. 3, and the results show that the battery exhibits very appreciable reversible specific capacity at different current densities. The cycle performance graph of this example is shown in fig. 4, and it can be clearly observed that the material has made a significant advance in both cycle life and rate performance. An SEM image of the surface of the zinc cathode after the battery prepared in the embodiment is subjected to constant current cycle test for 500 circles under the current density of 1A/g is shown in FIG. 5, and it can be clearly seen that Zn is contained in the battery in the cycle process 2+ And (3) uniformly redepositing on the surface of the Zn negative electrode, so that a layer of uniform Zn nanosheet is covered on the surface of the zinc foil. Fig. 6 is a scanning electron microscope image of the negative electrode modifier in example 1 of the present invention, and it can be seen that the negative electrode modifier prepared by the present invention has a "tea-like" lamellar structure, and due to its special spatial structure, it can sufficiently play a role in protecting the zinc negative electrode by reasonable surface recombination. Fig. 7 is a composition spectrum of elements in the negative electrode modifier in example 1 of the present invention, and it can be seen that the negative electrode modifier contains a plurality of effective elements in addition to two elements of Al and Au which are required to be added for the test.
Example 2
The embodiment provides a preparation method of a negative electrode modifier, which comprises the following steps:
cleaning long thorns and villi on the surface of the cactus, cutting off 3cm to obtain a cactus section after surface treatment, and sequentially freezing the cactus section after surface treatment at-40 ℃ for 24h, freeze-drying for 20h and grinding to obtain cactus powder.
The embodiment also provides a preparation method of the water-based zinc ion battery, and the water-based new ion battery comprises a negative plate, and the negative plate is obtained by the preparation method of the negative electrode modifier. Wherein. The preparation method of the water system zinc ion battery comprises the following steps:
(1) In a first solvent NMP, the following steps of (1) dissolving an aqueous zinc ion positive electrode active material alpha-manganese dioxide, a positive electrode conductive agent acetylene black and a positive electrode binder PVDF in a first solvent NMP according to a ratio of 7:2:1, mixing the materials by a ball mill to obtain anode slurry, coating the anode slurry on a titanium foil of an anode current collector, performing vacuum drying at 80 ℃ for 24 hours, removing a solvent, and finally punching the anode slurry into an anode sheet with the diameter of 12mm by a sheet cutter for later use; ball-milling and mixing a negative electrode modifier, a negative electrode conductive agent acetylene black and a negative electrode binder PVDF in a third NMP by using a ball mill to obtain a negative electrode slurry, coating the negative electrode slurry on a 0.05mm negative electrode current collector zinc foil, drying and pressurizing to obtain a negative electrode sheet;
(2) Mixing the positive plate and the negative plate in the step (1), the glass fiber diaphragm and electrolyte ZnSO 4 (2 mol/L)/MnSO 4 (0.2 mol/L) was assembled to obtain an aqueous zinc ion battery.
Example 3
The embodiment provides a preparation method of a negative electrode modifier, which comprises the following steps:
cleaning long thorns and villi on the surface of the cactus, cutting off 6cm to obtain a cactus section after surface treatment, and sequentially performing freezing treatment at the temperature of-60 ℃ for 6h, freeze-drying treatment for 40h and grinding treatment on the cactus section after surface treatment to obtain the negative electrode modifier.
The embodiment also provides a preparation method of the water-based zinc ion battery, and the water-based new ion battery comprises a negative plate, and the negative plate is obtained by the preparation method of the negative electrode modifier. Wherein. The preparation method of the water system zinc ion battery comprises the following steps:
(1) In a first solvent NMP, the following steps of (1) dissolving an aqueous zinc ion positive electrode active material alpha-manganese dioxide, a positive electrode conductive agent acetylene black and a positive electrode binder PVDF in a first solvent NMP according to a ratio of 7:2:1, mixing the materials by a ball mill to obtain anode slurry, coating the anode slurry on a titanium foil of an anode current collector, performing vacuum drying at 80 ℃ for 24 hours, removing a solvent, and finally punching the anode slurry into an anode sheet with the diameter of 12mm by a sheet cutter for later use; ball-milling and mixing a negative electrode modifier, a negative electrode conductive agent acetylene black and a negative electrode binder PVDF in a third NMP by using a ball mill to obtain a negative electrode slurry, coating the negative electrode slurry on a 0.05mm negative electrode current collector zinc foil, drying and pressurizing to obtain a negative electrode sheet;
(2) Mixing the positive plate and the negative plate in the step (1), the glass fiber diaphragm and electrolyte ZnSO 4 (2 mol/L)/MnSO 4 (0.2 mol/L)Assembling to obtain the water-based zinc ion battery.
Example 4
This example was carried out under the same conditions as in example 1 except that the temperature of the freezing treatment in the method for producing the negative electrode modifier was changed to-20 ℃.
Example 5
This example was carried out under the same conditions as in example 1 except that the time for the lyophilization treatment in the method for producing the negative electrode modifier was changed to 18 hours.
Example 6
In this example, except that the negative electrode modifier, the acetylene black conductive agent, and PVDF in step (1) of the preparation method of the aqueous zinc ion battery were mixed in the following ratio of 7:2: the mass ratio of 1 is replaced by 8:1: except for 1, the conditions are the same as those of the example 1, the rate performance graph of the zinc ion battery in the example is shown in fig. 8, and the reversible specific capacities of the battery with the negative electrode modifier in the example under different current densities are shown.
Example 7
In this example, the conditions were the same as in example 1 except that the positive electrode active material α -manganese dioxide was replaced with δ -manganese dioxide in step (1) of the method for producing an aqueous zinc ion battery, and the rate performance of the zinc ion battery in this example is shown in fig. 9, which shows the reversible specific capacities of the batteries having the negative electrode modifier of this example at different current densities.
Example 8
Except that the conductive agent acetylene black in the step (1) in the preparation method of the water-based zinc ion battery is replaced by ketjen black in the embodiment, the other conditions are the same as those in the embodiment 1, the rate performance graph of the zinc ion battery in the embodiment is shown in fig. 10, and the reversible specific capacity of the battery with the negative electrode modifier in the embodiment under different current densities is shown.
Example 9
This example eliminates the step (2) of ZnSO in the production method of an aqueous Zinc ion Battery 4 (2 mol/L)/MnSO 4 (0.2 mol/L) of the electrolyte was replaced with 2 mol/L of Zn (CF) 3 SO 3 ) 2 Otherwise, the conditions were the same as in example 1, which is a double of that of the zinc ion battery in this comparative exampleThe rate performance graph is shown in fig. 11, which shows the reversible specific capacity of the battery with the negative electrode modifier of this example at different current densities.
Comparative example 1
The comparative example provides a preparation method of a negative plate, and 0.05mm zinc foil is punched into a negative plate with the diameter of 16mm by a cutting machine. The method for producing the aqueous zinc ion battery was the same as in example 1. The rate performance graph of the zinc ion battery in this comparative example is shown in fig. 12, which shows the reversible specific capacity of the battery with the negative electrode modifier of this example at different current densities. The sequential performance chart of the zinc ion battery in the comparative example is shown in fig. 13, and it can be observed that the battery with the negative electrode modifier of the embodiment is 1A g -1 Long cycle life at high current density. The SEM image of the surface of the zinc negative electrode after 500 cycles of the constant current cycle test of the cell in this comparative example at a current density of 1A/g is shown in fig. 14, and it can be seen that significant zinc dendrites appear on the surface of the negative electrode in addition to the presence of flaky Zn, and these dendrites may puncture the separator during repeated charge and discharge cycles, causing a short circuit in the cell.
Comparative example 2
The comparative example was carried out under the same conditions as in example 1 except that the cactus sections were not lyophilized but air-dried.
Comparative example 3
In the comparative example, when the cactus segments are prepared, the freezing treatment and the freeze-drying treatment are not carried out, the negative electrode modifier is obtained by directly grinding, and other conditions are the same as those in the example 1.
The electrochemical performance of the zinc ion batteries corresponding to examples 1 to 9 and comparative examples 1 to 3 was tested, the current densities set for rate charging and discharging were 0.1A/g, 0.2A/g, 0.5A/g, 1A/g and 2A/g, for comparison, the test results are shown in table 1, wherein the electrolyte used was 50 μ L, and the rate of the battery was tested after standing for 24 hours.
TABLE 1
As can be seen from the above table, by comparing the example 1 with the example 4, in the same effective time, the insufficient freezing temperature easily causes the water in the sample not to be completely solidified in the effective time, which affects the next freeze-drying operation, and causes the loss of components or the structural collapse of the sample, thereby affecting the performance of the final material;
comparing example 1 with example 5, it can be seen that when the freeze-drying time is too short to allow the crystal water in the material to be completely sublimated, the final performance of the product is affected;
comparing example 1 and example 6, it is known that when the total amount of the negative electrode modifier of the aqueous zinc ion battery is adjusted, the rate performance of the battery is obviously changed, wherein the mass ratio of the negative electrode modifier, the acetylene black conductive agent and the PVDF is 7:2:1 is a preferred ratio;
it can be seen from the comparison between examples 1 and 7 that the battery has more excellent rate capability when the modified negative electrode is used, and when the positive electrode is made of alpha-manganese dioxide than when the positive electrode is made of delta-manganese dioxide;
comparing example 1 with example 8, it is seen that when the aqueous zinc ion battery negative electrode modifier is acetylene black or ketjen black as a conductive agent, the battery has similar high rate performance. When the conductive agent is acetylene black, the small rate performance of the battery is more excellent;
by comparing example 1 with example 9, znSO was used 4 (2 mol/L)/MnSO 4 (0.2 mol/L) electrolyte ratio 2 mol/L Zn (CF) was used 3 SO 3 ) 2 The electrolyte has better rate performance;
comparing example 1 with comparative example 1, it is clear that the battery of the aqueous zinc ion battery negative electrode modifier of the invention has more excellent rate and cycle performance. In addition, after the battery using the negative electrode modifier is subjected to long circulation with high current density, the new redeposition process of the negative electrode is more uniform, and a large amount of zinc dendrites capable of penetrating through the diaphragm are generated on the surface of the original zinc negative electrode without modification;
as can be seen by comparing the example 1 with the comparative example 2, the original components can be maintained to the maximum extent by the freeze-drying treatment, and the oxidation, the conversion of the nutritional components and the state change in the drying process can be effectively prevented, so that the required target product can be obtained, and the required modification effect can be finally achieved;
as is clear from comparison between example 1 and comparative example 3, the active ingredient is likely to be lost during the cycle when the moisture in the material is not treated, and the final effect of protecting the negative electrode is not obtained.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a negative electrode modifier is characterized by comprising the following steps: and sequentially freezing, freeze-drying and grinding the pretreated cactus sections to obtain the negative electrode modifier.
2. The method of claim 1, wherein the pre-treating comprises cleaning the surface of the cactus;
the cutting length of the cactus section is 3-6 cm.
3. The method for preparing the material according to claim 1, wherein the temperature of the freezing is-40 to-60 ℃;
the freezing time is 6 to 24h;
the freeze-drying time is 20 to 40h;
the particle size of the negative electrode modifier is 60-90 mu m.
4. An anode modifier, characterized in that it is prepared by the method for preparing an anode modifier according to any one of claims 1 to 3.
5. A negative electrode sheet comprising a negative electrode current collector and a negative electrode active layer disposed on the negative electrode current collector, wherein the negative electrode active layer comprises a negative electrode conductive agent, a negative electrode binder, and the negative electrode modifier of claim 4.
6. The negative electrode sheet according to claim 5, wherein the negative electrode conductive agent comprises any one of or a combination of at least two of Super P, acetylene black, or Ketjen black;
the negative electrode binder comprises PVDF;
the mass ratio of the negative electrode modifier to the negative electrode conductive agent to the negative electrode binder is (6.5-7.5) to (1.5-2.5) to 1;
the negative current collector includes a zinc foil.
7. An aqueous zinc-ion battery characterized by comprising the negative electrode sheet according to claim 5 or 6.
8. A method for producing an aqueous zinc-ion battery according to claim 7, characterized by comprising the steps of:
(1) Mixing a negative electrode modifier, a negative electrode conductive agent and a negative electrode binder in a solvent to obtain negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, and drying and pressurizing to obtain a negative electrode sheet;
(2) And (3) assembling the negative plate in the step (1), a positive plate, a diaphragm and electrolyte to obtain the water-based zinc ion battery.
9. The method according to claim 8, wherein the solvent of step (1) comprises NMP;
the mixing in the step (1) is carried out in a ball mill;
the mixing time in the step (1) is 25-35min;
the drying temperature in the step (1) is 55 to 65 ℃;
the pressurizing pressure in the step (1) is 5 to 15MPa.
10. The method of manufacturing according to claim 8, wherein the separator of step (2) comprises a glass fiber separator;
the electrolyte comprises ZnSO 4 /MnSO 4 Solution or Zn (CF) 3 SO 3 ) 2 A solution;
the ZnSO 4 /MnSO 4 ZnSO in solution 4 The concentration of the solution is 1 to 5mol/L;
the ZnSO 4 /MnSO 4 MnSO in solution 4 The concentration of the solution is 0.1 to 0.5mol/L;
the Zn (CF) 3 SO 3 ) 2 The concentration of the solution was 1 to 3mol/L.
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