CN107275601B - Aromatic hyperconjugated dicarboxylate and application of graphene composite material thereof - Google Patents
Aromatic hyperconjugated dicarboxylate and application of graphene composite material thereof Download PDFInfo
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- CN107275601B CN107275601B CN201710409203.XA CN201710409203A CN107275601B CN 107275601 B CN107275601 B CN 107275601B CN 201710409203 A CN201710409203 A CN 201710409203A CN 107275601 B CN107275601 B CN 107275601B
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 165
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 125000003118 aryl group Chemical group 0.000 title abstract description 28
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 68
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 66
- YDPPRPIIZGLGCJ-UHFFFAOYSA-N diphenyl butanedioate Chemical compound C=1C=CC=CC=1OC(=O)CCC(=O)OC1=CC=CC=C1 YDPPRPIIZGLGCJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000007773 negative electrode material Substances 0.000 claims abstract description 41
- 239000004305 biphenyl Substances 0.000 claims abstract description 14
- -1 diphenyl potassium Chemical compound 0.000 claims abstract description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 10
- 239000010406 cathode material Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- 239000012086 standard solution Substances 0.000 claims description 60
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 21
- CTTHAYDUZMEYLD-UHFFFAOYSA-N 1,1'-biphenyl;formic acid Chemical compound OC=O.OC=O.C1=CC=CC=C1C1=CC=CC=C1 CTTHAYDUZMEYLD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- JMZOMFYRADAWOG-UHFFFAOYSA-N methyl 7-methoxy-4-(7-methoxy-5-methoxycarbonyl-1,3-benzodioxol-4-yl)-1,3-benzodioxole-5-carboxylate Chemical compound COC(=O)C1=CC(OC)=C2OCOC2=C1C1=C2OCOC2=C(OC)C=C1C(=O)OC JMZOMFYRADAWOG-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- NEQFBGHQPUXOFH-UHFFFAOYSA-L 4-(4-carboxylatophenyl)benzoate Chemical compound C1=CC(C(=O)[O-])=CC=C1C1=CC=C(C([O-])=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-L 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- OONPLQJHBJXVBP-UHFFFAOYSA-N 3-(2-phenylethenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1C(O)=O OONPLQJHBJXVBP-UHFFFAOYSA-N 0.000 claims 2
- 229910052700 potassium Inorganic materials 0.000 abstract description 65
- 239000011591 potassium Substances 0.000 abstract description 62
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 56
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 238000009830 intercalation Methods 0.000 abstract description 3
- 125000006267 biphenyl group Chemical group 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 24
- ASYHSVJXTNYDOF-UHFFFAOYSA-L dipotassium 4-(4-carboxylatophenyl)benzoate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=C(C=C1)C1=CC=C(C=C1)C([O-])=O ASYHSVJXTNYDOF-UHFFFAOYSA-L 0.000 description 21
- 239000002244 precipitate Substances 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 238000011065 in-situ storage Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- LRUDDHYVRFQYCN-UHFFFAOYSA-L dipotassium;terephthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 LRUDDHYVRFQYCN-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- RCRBCNZJGBTYDI-UHFFFAOYSA-L dilithium;terephthalate Chemical compound [Li+].[Li+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 RCRBCNZJGBTYDI-UHFFFAOYSA-L 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- PVXCQHHWNDJIJP-UHFFFAOYSA-N 2,3-diphenylbutanedioic acid Chemical compound C=1C=CC=CC=1C(C(=O)O)C(C(O)=O)C1=CC=CC=C1 PVXCQHHWNDJIJP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XKAVPYJEHWWECE-UHFFFAOYSA-N C(=O)OC1=CC=CC=C1.C(=O)OC1=CC=CC=C1 Chemical compound C(=O)OC1=CC=CC=C1.C(=O)OC1=CC=CC=C1 XKAVPYJEHWWECE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000012296 anti-solvent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- QSLAXVNITWRIGL-UHFFFAOYSA-N [K].C1(=CC=C(C=C1)C(=O)O)C1=CC=C(C=C1)C(=O)O Chemical compound [K].C1(=CC=C(C=C1)C(=O)O)C1=CC=C(C=C1)C(=O)O QSLAXVNITWRIGL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- WGWWKACBPIVNDI-UHFFFAOYSA-N potassium;stilbene Chemical compound [K].C=1C=CC=CC=1C=CC1=CC=CC=C1 WGWWKACBPIVNDI-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
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- H01M4/364—Composites as mixtures
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention relates to the technical field of negative electrode materials of potassium ion batteries, and aims to solve the technical problem that the prior potassium ion battery is poor in multiplying power performance and poor in cycling stability. The invention provides an aromatic hyperconjugated dicarboxylate and application of a graphene composite material thereof. The aromatic hyperconjugated dicarboxylate and the graphene composite material thereof comprise 4,4 ' diphenyl dicarboxylate, 4 ' diphenyl ethylene dicarboxylate and 4,4 ' diphenyl potassium dicarboxylate/graphene composite material (K)2BPDC @ GR) and potassium 4, 4' diphenylethylene dicarboxylate/graphene composite (K)2SBDC @ GR). The aromatic super-conjugated dicarboxylate and the graphene composite material thereof are used as a new family of potassium ion battery cathode materials, a reversible potassium ion de-intercalation platform is shown, the super-conjugated dicarboxylate has a larger pi-conjugated three-dimensional space and a faster potassium ion and electron transmission channel, has high theoretical specific capacity, and can realize higher rate performance.
Description
Technical Field
The invention relates to the technical field of negative electrode materials of potassium ion batteries, in particular to an aromatic hyperconjugated dicarboxylate and application of a graphene composite material thereof.
Background
Energy is the material basis of human production and life, and is closely related to human civilization and technical progress. With the continuous development of human civilization and world economy, human beings face the dual challenges of resource exhaustion and increasingly worsened living environment. In recent years, the traditional fossil energy causes huge pollution to the environment, and the energy and environmental problems become prominent problems which hinder the survival and development of human beings. The method has the advantages of adjusting and optimizing the energy structure, developing new energy which can be recycled and has no pollution to the environment, and has very important significance. New energy sources currently available for development include: wind, solar, water, nuclear, tidal, and the like. The storage of these clean secondary energy sources requires a complete and unified theoretical basis and has many scientific and technical problems to be solved.
Lithium ion batteries are of great interest because of their flexibility, freedom from geographical constraints and high efficiency. The lithium ion battery stores and converts energy mainly according to mutual conversion of chemical energy and electric energy of an electrode material, and is widely applied to energy storage devices such as notebooks, cameras, mobile phones and the like commonly used in aerospace, electric automobiles and daily life. However, due to the depletion of lithium resources and the disadvantages of the currently commercialized inorganic lithium ion batteries, especially the pollution of the environment, the high cost and the use of non-renewable resources due to the use of transition metals, it is far from meeting the requirements of people for clean energy. In recent years, a variety of new alternatives to secondary batteries have been developed, mainly including sodium ion batteries and potassium ion batteries. The potassium ion battery has the following advantages: the potassium resource is rich in the crust; the price is low; the electrochemical activity of the electrolyte of the potassium ion battery is high; potassium ion batteries have a standard reduction potential similar to that of lithium ion batteries. The currently reported negative electrode materials of the potassium ion battery are few, and mainly comprise a plurality of electrodeless negative electrode materials, carbon materials and organic negative electrode materials. Due to the large radius of potassium ions, the electrodeless negative electrode material can have irreversible structural collapse in the charging and discharging process, so that the rate performance is low and the cycle stability is poor; the carbon material has lower de-intercalation potassium potential and is easy to form dendrite to cause potential safety hazard; the organic negative electrode material has the advantages of wide source, flexibility, foldability, designable chemical structure, biodegradability, stable structure, proper chemical potassium-deintercalation platform, large specific capacity and the like, and is most suitable for potassium ion batteries. The currently commonly used organic anode material of the potassium ion battery is mainly aromatic dicarboxylic acid salt, but the rate performance is worried.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provide an aromatic super-conjugated dicarboxylate with good rate capability and capable of being used as a negative electrode material of a potassium ion battery and application of the graphene composite material.
The purpose of the invention is realized by the following technical scheme:
the application of the aromatic super-conjugated dicarboxylate as a negative electrode material of a potassium ion battery.
Further, in the application of the aromatic hyperconjugated dicarboxylate as the negative electrode material of the potassium ion battery, the aromatic hyperconjugated dicarboxylate is 4, 4' biphenyl dicarboxylate (R)2BPDC) or 4, 4' diphenylethylene dicarboxylate (R)2SBDC) having the chemical formula:
wherein, the R group is any one or two of alkali metal, alkaline earth metal or transition metal.
Further, in the application of the aromatic hyperconjugated dicarboxylate as a potassium ion battery negative electrode material, the R group is one or two of K, Mg, Ga, Ba, Mn, Fe, Co, Ni, Cu, Zn, Al or Ag.
The application of the aromatic super-conjugated dicarboxylate/graphene composite material as a potassium ion battery negative electrode material.
The 4, 4' -biphenyl diformate/graphene composite material is used as a potassium ion battery negative electrode material.
Further, in the application of the 4,4 'biphenyl diformate/graphene composite material as a negative electrode material of a potassium ion battery, the 4, 4' biphenyl diformate/graphene composite material is obtained by the following steps of:
A. preparing a series of solutions: weighing a plurality of parts of 4, 4' -biphenyl diformate with different masses, and preparing a plurality of series standard solutions with sequentially increasing concentrations by using deionized water;
B. selecting a standard solution: dropwise adding all the series of standard solutions into absolute ethyl alcohol or N-methyl pyrrolidone respectively, wherein the volume ratio of the standard solutions to the absolute ethyl alcohol or the N-methyl pyrrolidone is 1:10, and selecting the series of standard solutions which can just enable the absolute ethyl alcohol or the N-methyl pyrrolidone to generate precipitation from all the series of standard solutions to obtain a standard solution, wherein the concentration of the standard solution is S mg/L;
C. determining the concentration of the reaction solution, the dosage of absolute ethyl alcohol or N-methyl pyrrolidone and the dosage of graphene: preparing a reaction solution with the concentration of X mL being higher than that of a standard solution, wherein the concentration of the reaction solution is F mg/mL; the amount of graphene used (mg) ═ X (F-S) × 0.05; determining the dosage of the absolute ethyl alcohol or the N-methyl pyrrolidone according to the volume ratio of the reaction solution to the absolute ethyl alcohol or the N-methyl pyrrolidone being 1: 10;
d, preparing a 4, 4' -biphenyl diformate/graphene composite material:
(1) uniformly stirring graphene and absolute ethyl alcohol or N-methyl pyrrolidone to obtain a uniform mixed solution;
(2) dropwise adding a reaction solution into the mixed solution under a stirring state to obtain a suspension;
(3) and stirring the turbid liquid, carrying out solid-liquid separation, washing and drying to obtain the 4, 4' biphenyl diformate/graphene composite material.
Further, the 4, 4' biphenyl diformate/graphene composite material is used as a potassium ion battery negative electrode material, and the concentrations of a plurality of series of standard solutions with sequentially increasing concentrations in the step A are respectively 2mg/mL, 3mg/mL, 5mg/mL, 10mg/mL and 20 mg/mL; all stirring in the step D adopts ultrasonic stirring, and the time of all ultrasonic stirring is 2-4 h; and D, performing suction filtration or centrifugation as solid-liquid separation in the step (3) in the step D, wherein the washing is washing by adopting absolute ethyl alcohol, the drying is vacuum drying, the vacuum drying time is 12-24h, and the temperature is 80-120 ℃.
The 4, 4' -diphenylethylene dicarboxylate/graphene composite material is used as a potassium ion battery cathode material.
Further, the 4,4 'diphenyl ethylene dicarboxylate/graphene composite material is used as a potassium ion battery cathode material, and the 4, 4' diphenyl ethylene dicarboxylate/graphene composite material is obtained through the following steps of:
A. preparing a series of solutions: weighing a plurality of parts of 4, 4' -diphenylethylene dicarboxylate with different masses, and preparing a plurality of series standard solutions with sequentially increasing concentrations by using deionized water;
B. selecting a standard solution: dropwise adding all the series of standard solutions into absolute ethyl alcohol or N-methyl pyrrolidone respectively, wherein the volume ratio of the standard solutions to the absolute ethyl alcohol or the N-methyl pyrrolidone is 1:10, and selecting the series of standard solutions which can just enable the absolute ethyl alcohol or the N-methyl pyrrolidone to generate precipitation from all the series of standard solutions to obtain a standard solution, wherein the concentration of the standard solution is S mg/L;
C. determining the concentration of the reaction solution, the dosage of absolute ethyl alcohol or N-methyl pyrrolidone and the dosage of graphene: preparing a reaction solution with the concentration of X mL being higher than that of a standard solution, wherein the concentration of the reaction solution is F mg/mL; the amount of graphene used (mg) ═ X (F-S) × 0.05; determining the dosage of the absolute ethyl alcohol or the N-methyl pyrrolidone according to the volume ratio of the reaction solution to the absolute ethyl alcohol or the N-methyl pyrrolidone being 1: 10;
d, preparing a 4, 4' diphenyl ethylene dicarboxylate/graphene composite material:
(1) uniformly stirring graphene and absolute ethyl alcohol or N-methyl pyrrolidone to obtain a uniform mixed solution;
(2) dropwise adding a reaction solution into the mixed solution under a stirring state to obtain a suspension;
(3) and stirring the turbid liquid, carrying out solid-liquid separation, washing and drying to obtain the 4, 4' diphenylethylene dicarboxylate/graphene composite material.
Further, the 4, 4' diphenylethylene dicarboxylate/graphene composite material is used as a potassium ion battery negative electrode material, and the concentrations of a plurality of series of standard solutions with sequentially increasing concentrations in the step A are respectively 2mg/mL, 3mg/mL, 5mg/mL, 10mg/mL and 20 mg/mL; all stirring in the step D adopts ultrasonic stirring, and the time of all ultrasonic stirring is 2-4 h; and D, performing suction filtration or centrifugation as solid-liquid separation in the step (3) in the step D, wherein the washing is washing by adopting absolute ethyl alcohol, the drying is vacuum drying, the vacuum drying time is 12-24h, and the temperature is 80-120 ℃.
Compared with the prior art, the invention has the beneficial effects that: according to the aromatic hyperconjugated dicarboxylate and the graphene composite material thereof, the hyperconjugated dicarboxylate obtained by expanding an aromatic skeleton, namely 4,4 'diphenyl dicarboxylate or 4, 4' diphenyl ethylene dicarboxylate, is used as a negative electrode material of a potassium ion battery, and has good electrochemical performance; after the graphene composite material is prepared from the graphene and the graphene by the method, the electrochemical performance of the graphene composite material is good; theoretically, the aromatic super-conjugated dicarboxylate and the graphene composite material thereof, which are disclosed by the invention, are used as a new family of potassium ion battery cathode materials, show a reversible potassium ion de-intercalation platform, and the super-conjugated dicarboxylate has a larger pi-conjugated three-dimensional space, a faster potassium ion and electron transmission channel, has high theoretical specific capacity, and can realize higher rate capability; the synthetic method is simple, low in solubility in electrolyte, green and environment-friendly, and can be used for preparing flexible batteries; the method has very important significance as a new family of potassium ion batteries, and can effectively solve the problems of resource shortage of electrode materials of lithium ion batteries, environmental pollution caused by use of transition metals, poor rate capability of potassium ion batteries and the like.
Drawings
FIG. 1 Potassium 4, 4' -biphenyldicarboxylate (K) according to the invention2BPDC) and potassium 4, 4' -diphenylethylene dicarboxylate (K)2SBDC) structure and its redox mechanism.
FIG. 2a Potassium 4, 4' Biphenyldiformate (K) according to the invention2BPDC) of1H NMR spectrum.
FIG. 2b Potassium 4, 4' Biphenyldiformate (K) according to the invention2BPDC).
FIG. 2c Potassium 4, 4' Biphenyldiformate (K) according to the invention2BPDC).
FIG. 3a Potassium 4, 4' Biphenyldiformate (K) according to the invention2BPDC).
FIG. 3b Potassium 4, 4' Biphenyldiformate (K) according to the invention2BPDC).
FIG. 4a Potassium 4, 4' Diphenyl Ethylene dicarboxylate (K) according to the invention2SBDC) of1H NMR spectrum.
FIG. 4b Potassium 4, 4' diphenylethylene dicarboxylate (K) of the present invention2SBDC) was used.
FIG. 4c Potassium 4, 4' diphenylethylene dicarboxylate (K) of the present invention2SBDC).
FIG. 5a Potassium 4, 4' Diphenyl Ethylene dicarboxylate (K) according to the invention2SBDC).
FIG. 5b Potassium 4, 4' diphenylethylene dicarboxylate (K) of the present invention2SBDC).
FIG. 6a Potassium 4, 4' Biphenyldiformate (K) according to the invention2BPDC) and 4, 4' potassium bifendate/graphene composite material (K)2BPDC @ GR).
FIG. 6b Potassium 4, 4' Diphenyl Ethylene dicarboxylate (K) according to the invention2SBDC) and 4, 4' -diphenylethylene potassium dicarboxylate/graphene composite material (K)2Comparison of XRD patterns of SBDC @ GR).
FIG. 7a Potassium 4, 4' Biphenyldiformate/graphene composite (K) of the invention2BPDC @ GR).
FIG. 7b Potassium 4, 4' Diphenyl Ethylene dicarboxylate/graphene composite (K) of the present invention2SBDC @ GR).
FIG. 8a Potassium 4, 4' Biphenyldiformate (K) according to the invention2BPDC).
FIG. 8b potassium 4, 4' biphenyldicarboxylate/graphene composite (K) of the present invention2BPDC @ GR).
FIG. 9a Potassium 4, 4' Biphenyldiformate (K) according to the invention2BPDC) at different current densities.
FIG. 9b potassium 4, 4' biphenyldicarboxylate/graphene composite (K) of the present invention2BPDC @ GR) at different current densities.
FIG. 10a Potassium 4, 4' Biphenyldiformate (K) according to the invention2BPDC) (a) at 20mA g-1Long cycle test pattern below.
FIG. 10b potassium 4, 4' biphenyldicarboxylate/graphene composite (K) of the present invention2BPDC/GR) at 50mA g-1Long cycle test pattern below.
FIG. 10c potassium 4, 4' biphenyldicarboxylate/graphene composite (K) of the present invention2BPDC/GR) at 1000mA g-1(c) Long cycle test pattern below.
FIG. 11a Potassium 4, 4' Diphenyl Ethylene dicarboxylate (K) according to the invention2SBDC).
FIG. 11b Potassium 4, 4' diphenylethylene dicarboxylate/graphene composite (K) of the present invention2SBDC @ GR).
FIG. 12a Potassium 4, 4' Diphenyl Ethylene dicarboxylate (K) according to the invention2SBDC) rate performance test plots at different current densities.
FIG. 12b Potassium 4, 4' Diphenyl Ethylene dicarboxylate/graphene composite (K) of the present invention2SBDC @ GR) under different current densities.
FIG. 13a Potassium 4, 4' Diphenyl Ethylene dicarboxylate (K) according to the invention2SBDC) at 20mA g-1Long cycle test pattern below.
FIG. 13b Potassium 4, 4' Diphenyl Ethylene dicarboxylate/graphene composite (K) of the present invention2SBDC @ GR) at 50mA g-1Long cycle test pattern below.
FIG. 14 is a graph of the rate capability test of the conductive additive SP of the present invention at different current densities.
FIG. 15a is a CV diagram of potassium terephthalate of the present invention.
FIG. 15b is a graph showing the actual specific capacity and capacity retention rate of potassium terephthalate of the present invention at different currents.
Detailed Description
The technical aspects of the present invention will be described in detail below with reference to examples, but it should be noted that the following are only preferred embodiments of the present invention, and technical features of the present invention may be combined with each other without contradiction. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications should fall within the scope of the invention.
The application of the aromatic super-conjugated dicarboxylate as a negative electrode material of a potassium ion battery.
Further, in the application of the aromatic hyperconjugated dicarboxylate as the negative electrode material of the potassium ion battery, the aromatic hyperconjugated dicarboxylate is 4, 4' biphenyl dicarboxylate (R)2BPDC) or 4, 4' diphenylethylene dicarboxylate (R)2SBDC) having the chemical formula:
wherein, the R group is any one or two of alkali metal, alkaline earth metal or transition metal.
Further, in the application of the aromatic hyperconjugated dicarboxylate as a potassium ion battery negative electrode material, the R group is one or two of K, Mg, Ga, Ba, Mn, Fe, Co, Ni, Cu, Zn, Al or Ag.
The application of the aromatic super-conjugated dicarboxylate/graphene composite material as a potassium ion battery negative electrode material.
The 4, 4' -biphenyl diformate/graphene composite material is used as a potassium ion battery negative electrode material.
Further, in the application of the 4,4 'biphenyl diformate/graphene composite material as a negative electrode material of a potassium ion battery, the 4, 4' biphenyl diformate/graphene composite material is obtained by the following steps of:
A. preparing a series of solutions: weighing a plurality of parts of 4, 4' -biphenyl diformate with different masses, and preparing a plurality of series standard solutions with sequentially increasing concentrations by using deionized water;
B. selecting a standard solution: dropwise adding all the series of standard solutions into absolute ethyl alcohol or N-methyl pyrrolidone respectively, wherein the volume ratio of the standard solutions to the absolute ethyl alcohol or the N-methyl pyrrolidone is 1:10, and selecting the series of standard solutions which can just enable the absolute ethyl alcohol or the N-methyl pyrrolidone to generate precipitation from all the series of standard solutions to obtain a standard solution, wherein the concentration of the standard solution is S mg/L;
C. determining the concentration of the reaction solution, the dosage of absolute ethyl alcohol or N-methyl pyrrolidone and the dosage of graphene: preparing a reaction solution with the concentration of X mL being higher than that of a standard solution, wherein the concentration of the reaction solution is F mg/mL; the amount of graphene used (mg) ═ X (F-S) × 0.05; determining the dosage of the absolute ethyl alcohol or the N-methyl pyrrolidone according to the volume ratio of the reaction solution to the absolute ethyl alcohol or the N-methyl pyrrolidone being 1: 10;
d, preparing a 4, 4' -biphenyl diformate/graphene composite material:
(1) uniformly stirring graphene and absolute ethyl alcohol or N-methyl pyrrolidone to obtain a uniform mixed solution;
(2) dropwise adding a reaction solution into the mixed solution under a stirring state to obtain a suspension;
(3) and stirring the turbid liquid, carrying out solid-liquid separation, washing and drying to obtain the 4, 4' biphenyl diformate/graphene composite material.
Further, the 4, 4' biphenyl diformate/graphene composite material is used as a potassium ion battery negative electrode material, and the concentrations of a plurality of series of standard solutions with sequentially increasing concentrations in the step A are respectively 2mg/mL, 3mg/mL, 5mg/mL, 10mg/mL and 20 mg/mL; all stirring in the step D adopts ultrasonic stirring, and the time of all ultrasonic stirring is 2-4 h; and D, performing suction filtration or centrifugation as solid-liquid separation in the step (3) in the step D, wherein the washing is washing by adopting absolute ethyl alcohol, the drying is vacuum drying, the vacuum drying time is 12-24h, and the temperature is 80-120 ℃.
The 4, 4' -diphenylethylene dicarboxylate/graphene composite material is used as a potassium ion battery cathode material.
Further, the 4,4 'diphenyl ethylene dicarboxylate/graphene composite material is used as a potassium ion battery cathode material, and the 4, 4' diphenyl ethylene dicarboxylate/graphene composite material is obtained through the following steps of:
A. preparing a series of solutions: weighing a plurality of parts of 4, 4' -diphenylethylene dicarboxylate with different masses, and preparing a plurality of series standard solutions with sequentially increasing concentrations by using deionized water;
B. selecting a standard solution: dropwise adding all the series of standard solutions into absolute ethyl alcohol or N-methyl pyrrolidone respectively, wherein the volume ratio of the standard solutions to the absolute ethyl alcohol or the N-methyl pyrrolidone is 1:10, and selecting the series of standard solutions which can just enable the absolute ethyl alcohol or the N-methyl pyrrolidone to generate precipitation from all the series of standard solutions to obtain a standard solution, wherein the concentration of the standard solution is S mg/L;
C. determining the concentration of the reaction solution, the dosage of absolute ethyl alcohol or N-methyl pyrrolidone and the dosage of graphene: preparing a reaction solution with the concentration of X mL being higher than that of a standard solution, wherein the concentration of the reaction solution is F mg/mL; the amount of graphene used (mg) ═ X (F-S) × 0.05; determining the dosage of the absolute ethyl alcohol or the N-methyl pyrrolidone according to the volume ratio of the reaction solution to the absolute ethyl alcohol or the N-methyl pyrrolidone being 1: 10;
d, preparing a 4, 4' diphenyl ethylene dicarboxylate/graphene composite material:
(1) uniformly stirring graphene and absolute ethyl alcohol or N-methyl pyrrolidone to obtain a uniform mixed solution;
(2) dropwise adding a reaction solution into the mixed solution under a stirring state to obtain a suspension;
(3) and stirring the turbid liquid, carrying out solid-liquid separation, washing and drying to obtain the 4, 4' diphenylethylene dicarboxylate/graphene composite material.
Further, the 4, 4' diphenylethylene dicarboxylate/graphene composite material is used as a potassium ion battery negative electrode material, and the concentrations of a plurality of series of standard solutions with sequentially increasing concentrations in the step A are respectively 2mg/mL, 3mg/mL, 5mg/mL, 10mg/mL and 20 mg/mL; all stirring in the step D adopts ultrasonic stirring, and the time of all ultrasonic stirring is 2-4 h; and D, performing suction filtration or centrifugation as solid-liquid separation in the step (3) in the step D, wherein the washing is washing by adopting absolute ethyl alcohol, the drying is vacuum drying, the vacuum drying time is 12-24h, and the temperature is 80-120 ℃.
Examples
Application of aromatic super-conjugated dicarboxylate as potassium ion battery negative electrode material
In order to illustrate the oxidation-reduction principle of aromatic hyperconjugated dicarboxylates in potassium ion batteries, the invention uses 4, 4' biphenyl diformate (R)2BPDC) and 4, 4' diphenylethylene dicarboxylate (R)2SBDC) as an example to illustrate its principles.
As shown in fig. 1-15 b. Specifically, as shown in FIG. 1, 4, 4' biphenyldicarboxylate (R) salt2BPDC) and 4, 4' diphenylethylene dicarboxylate (R)2SBDC) can be converted between an oxidation state and a reduction state through getting and losing 2mol of electrons, and has stronger stability because a larger conjugated surface has stronger ability of dispersing charges; however, as the conjugate plane increases, the steric resistance thereof also increases, which in turn adversely affects the ability to disperse charges and the stability thereof, and it is the starting point of the present invention to increase the conjugate plane while reducing the steric resistance.
Experiments show that the aromatic super-conjugated dicarboxylate containing two conjugated benzene rings has good electrochemical performance, and simultaneously, considering that graphene is sp-form carbon atoms2The honeycomb planar film formed by the hybridization mode is a quasi-two-dimensional material with the thickness of only one atomic layer, has good planarity, and can exert the performance of the aromatic hyperconjugated dicarboxylate of two conjugated benzene rings to the maximum extent and reduce the space resistance by preparing the composite material from the aromatic hyperconjugated dicarboxylate of the two conjugated benzene rings and Graphene (GR). The following is 4, 4' -biphenyldicarboxylate (R)2BPDC) and 4, 4' diphenylethylene dicarboxylate (R)2SBDC) and a composite material prepared from both and graphene, respectively, as an example, illustrate the use of the present invention as a negative ion material for a potassium ion battery.
Basic information of the experiment: 4,4 'Biphenyldicarboxylic acid, potassium 4, 4' diphenylethylene dicarboxylate, potassium hydroxide was purchased from Aladin.1HNMR used D at room temperature2O as solvent was tested on an AC Bruker spectrometer 400MHz with chemical shifts to residual H2Ppm in ppm of O; FT-IR adopts Fourier transform infrared spectrometer to test the wave number range of 400-3200cm-1(ii) a XRD test adopts Cu Ka radiation
X' Pert Pro MPD with sweep rate of 0.06 ° s-1The range of 2 theta diffraction angle is 5-80 degrees; TGA test was performed using a TA-Q50 thermogravimetric analyzer at N2Testing from room temperature to 600 ℃ at a heating rate of 10 ℃/min under an atmosphere; SEM test spectra were collected by FE-SEM, Hitachi, S3400N scanning electron microscope.
Bis, 4' -biphenyldicarboxylate (R)2BPDC), 4' diphenylethylene dicarboxylate (R)2SBDC) and application of composite material prepared by respectively compounding SBDC and SBDC with graphene as negative electrode material of potassium ion battery
The aromatic hyperconjugated dicarboxylate is 4, 4' -biphenyl dicarboxylate (R)2BPDC) or 4, 4' diphenylethylene dicarboxylate (R)2SBDC) having the chemical formula:
wherein, the R group is any one or two of alkali metal, alkaline earth metal or transition metal.
The R group is one or two of K, Mg, Ga, Ba, Mn, Fe, Co, Ni, Cu, Zn, Al or Ag.
The following 4, 4' -biphenyldicarbonic acid potassium (K)2BPDC) and potassium 4, 4' -diphenylethylene dicarboxylate (K)2SBDC) were prepared in the following manner, respectively.
1.4, 4' -Biphenyldiformate Potassium (K)2BPDC) preparation and characterization
4, 4' -Biphenyldiformate Potassium (K)2BPDC) was performed using 4, 4' -biphenyldicarboxylic acid and potassium hydroxide in a stoichiometric ratio of 1:2, and preparing the product. Namely, 20mmol of 95 percent 4, 4' biphenyldicarboxylic acid and 40mmol of potassium hydroxide are mixed according to the mol ratio of 1:2 and dissolved in 30mL deionized water or dissolved in 30mL mixed solution (deionized water and ethylene glycol according to the volumeMixing according to the ratio of 1: 1), firstly carrying out ultrasonic treatment for 1-1.5h, and stirring for 2-3h at the temperature of 60 ℃; then placed in a 150mL Shelank flask at N2Carrying out reflux reaction for 24-72h at 110 ℃ under protection; then, the solution after the reaction is dripped into 300mL of absolute ethyl alcohol or NMP anti-solvent dropwise and stirred, a large amount of white precipitate is generated, and the volume ratio of the positive solvent to the negative solvent is 1: 10. and carrying out suction filtration or high-speed centrifugal separation on the obtained white precipitate, washing for at least 3 times by using absolute ethyl alcohol, drying for 6-8h at the temperature of 60-80 ℃, and then carrying out vacuum drying for 12-24h at the temperature of 80-120 ℃ to obtain the product.
The product was characterized as shown in fig. 2 a-3 b.1H NMR measurement of the resulting white precipitate gave two distinct types of H signals on the corresponding biphenyl ring, δ, 7.67and 7.85ppm, see FIG. 2a, and FT-IR measurement of the resulting white precipitate gave COO in comparison with the FT-IR spectrum of the starting 4, 4' biphenyldicarboxylic acid-The vibrational peak had a significant peak shift and the-OH vibrational peak belonging to the COOH group disappeared, as shown in FIG. 2 b. XRD measurement showed that the obtained white precipitate was compared with the XRD pattern of 4,4 '-biphenyldicarboxylic acid as the starting material, and no diffraction peak of 4, 4' -biphenyldicarboxylic acid was observed, and new diffraction peak positions 2 θ of 6.14,15.53and 27.84 ° were observed, as shown in fig. 2 c.
The obtained white precipitate is 4, 4' -diphenyl dimethyl acid potassium (K)2BPDC) and has extremely high purity. TGA test can obtain the synthesized 4, 4' biphenyl potassium diformate (K)2BPDC) had excellent thermal stability, with a 5 wt% loss corresponding to a temperature of 578 ℃, see figure 3 a. SEM test gave potassium 4, 4' -biphenyldicarboxylate (K) prepared by back titration2BPDC) is a thin slice with a thickness in nm scale, see fig. 3 b.
In addition, when the R group is one or two of Mg, Ga, Ba, Mn, Fe, Co, Ni, Cu, Zn, Al, or Ag, the preparation method can still be prepared according to the method, and only the corresponding alkali and the amount thereof need to be adjusted accordingly, which is not described herein again.
2. 4, 4' -Diphenyl ethylene Potassium dicarboxylates (K)2SBDC) preparation and characterization
The method comprises the following specific steps: mixing 20mmol 95% 4, 4' -diphenylethylene dicarboxylic acid and 40mmol potassium hydroxide at a molar ratio of 1:2, dissolving in 30mL deionized water or 30mL mixed solution (deionized water and ethylene glycol are mixed at a volume ratio of 1: 1), performing ultrasonic treatment for 1-1.5h, and stirring at 60 deg.C for 2-3 h; then placed in a 150mL Shelank flask at N2Carrying out reflux reaction for 24-72h at 110 ℃ under protection; then, the solution after the reaction is dripped into 300mL of absolute ethyl alcohol or NMP anti-solvent dropwise and stirred, a large amount of white precipitate is generated, and the volume ratio of the positive solvent to the negative solvent is 1: 10. and carrying out suction filtration or high-speed centrifugal separation on the obtained white precipitate, washing for at least 3 times by using absolute ethyl alcohol, drying for 6-8h at the temperature of 60-80 ℃, and then carrying out vacuum drying for 12-24h at the temperature of 80-120 ℃ to obtain the product.
The product was characterized as shown in fig. 4 a-5 b.1The white precipitate obtained from the H NMR test gave three distinct classes of H signals, δ 7.55and 7.75ppm on the benzene ring and δ 7.25ppm on the olefin, respectively, as shown in FIG. 4a, and the white precipitate obtained from the FT-IR test gave a COO spectrum compared with the starting 4, 4' diphenylethylene dicarboxylic acid FT-IR spectrum-The vibrational peak had a significant peak shift and the-OH vibrational peak belonging to the COOH group disappeared, as shown in FIG. 4 b. XRD tests showed that the XRD pattern of the obtained white precipitate compared with that of 4,4 '-diphenylethylene dicarboxylic acid as the starting material showed no diffraction peak of 4, 4' -diphenylethylene dicarboxylic acid, and new diffraction peak positions 2 θ of 5.51,27.75and 33.37 ° were observed, as shown in fig. 4 c. The white precipitate obtained is 4, 4' -diphenylethylene potassium dicarboxylate (K)2SBDC) and has extremely high purity. TGA test gave the synthesized potassium 4, 4' -diphenylethylene dicarboxylate (K)2SBDC) had excellent thermal stability, with a 5 wt% loss corresponding to a temperature of 542 ℃, see figure 5 a. SEM test gave potassium 4, 4' -diphenylethylene dicarboxylate (K) prepared by back titration2SBDC) is a thin slice with a thickness in the nm scale, see fig. 5 b.
In addition, when the R group is one or two of Mg, Ga, Ba, Mn, Fe, Co, Ni, Cu, Zn, Al, or Ag, the preparation method can still be prepared according to the method, and only the corresponding alkali and the amount thereof need to be adjusted accordingly, which is not described herein again.
3. 4, 4' potassium bifendate/graphene composite material (K)2Preparation of BPDC @ GR)
4, 4' potassium bifendate/graphene composite material (K)2BPDC @ GR) is prepared by the following specific steps:
weighing a certain mass of 4, 4' -biphenyl potassium diformate (K)2BPDC) respectively dissolved in a certain volume of deionized water to prepare a series of solutions with the concentrations of 2mg/mL, 3mg/mL, 5mg/mL, 10mg/mL and 20mg/mL, then respectively taking 1mL of the solution and dropwise adding the solution into 10mL of absolute ethyl alcohol under stirring to see whether a precipitate is generated or not, recording the concentration of the solution when the precipitate is initially generated as A mol/mL, and then preparing 30mL of 4, 4' potassium bifendate (K) with a certain concentration of B mol/mL and a certain concentration higher than A concentration2BPDC) to obtain 4, 4' -biphenyldicarboxylate (K)2BPDC) aqueous solution for standby, weighing 30 x (B-A) 5% graphene, placing the graphene in a 500mL flask, adding 300mL absolute ethyl alcohol, ultrasonically stirring for 2-4h, then dropwise back-titrating 30mL B concentration hyperconjugated potassium dicarboxylate aqueous solution obtained by expanding an aromatic skeleton into ultrasonically stirred uniform graphene absolute ethyl alcohol, stirring to obtain a suspension, and ultrasonically stirring the obtained suspension for 2-4h again to enable 4, 4' potassium bifendate (K)2BPDC) enters a graphene interlayer and is evenly compounded in situ, then suspension is subjected to suction filtration or high-speed centrifugal separation and is washed in absolute ethyl alcohol for at least 3 times, the suspension is dried for 6 to 8 hours at the temperature of between 60 and 80 ℃, and then is dried for 12 to 24 hours in vacuum at the temperature of between 80 and 120 ℃, and 4, 4' potassium bifluoride (K) is finally obtained2BPDC) and GR as K2BPDC@GR。
4. 4, 4' -Diphenyl ethylene potassium dicarboxylates/graphene composite (K)2Preparation of SBDC @ GR)
The preparation method comprises the following steps: weighing a certain mass of 4, 4' -diphenylethylene potassium dicarboxylate, respectively dissolving in a certain volume of deionized water to prepare a series of solutions with the concentrations of 2mg/mL, 3mg/mL, 5mg/mL, 10mg/mL and 20mg/mL, respectively dropwise adding 1mL of the solutions into 10mL of absolute ethyl alcohol under stirring to see whether precipitates are generated or not, and recording the solution content when the precipitates are initially generatedMarking the concentration as A mol/mL, preparing 30mL of 4,4 'potassium diphenylene dicarboxylate aqueous solution with a certain concentration of B mol/mL and higher than A concentration for later use, weighing 30X (B-A) 5% of graphene, placing the graphene in a 500mL flask, adding 300mL of absolute ethyl alcohol, ultrasonically stirring for 2-4h, dropwise and back-titrating two types of hyperconjugated potassium dicarboxylate aqueous solutions with B concentration obtained by expanding an aromatic skeleton into the absolute ethyl alcohol of the uniformly ultrasonically stirred graphene, stirring to obtain a suspension, ultrasonically stirring the obtained suspension for 2-4h again to enable the 4, 4' potassium diphenylene dicarboxylate to enter a graphene interlayer and to be uniformly compounded in situ, performing suction filtration or high-speed centrifugal separation on the suspension, washing the suspension for at least 3 times by using the absolute ethyl alcohol, drying at 60-80 ℃ for 6-8h, then drying at 80-120 ℃ for 12-24h in vacuum to finally obtain the in-situ composite material of 4, 4' diphenyl ethylene potassium dicarboxylate and GR, which is marked as K2SBDC@GR。
5. 4, 4' potassium bifendate/graphene composite material (K)2BPDC @ GR) and potassium 4, 4' diphenylethylene dicarboxylate/graphene composite (K)2Characterization of SBDC @ GR)
As shown in FIGS. 6a and 6b, 4, 4' Biphenyldicarboxylic acid Potassium/graphene composite (K)2BPDC @ GR) and potassium 4, 4' diphenylethylene dicarboxylate/graphene composite (K)2SBDC @ GR) retains the crystal structure characteristics of potassium 4,4 'diphenyldicarboxylate and potassium 4, 4' diphenylethylene dicarboxylate, respectively, so that the two composites do not affect the performance of potassium 4,4 'diphenyldicarboxylate and potassium 4, 4' diphenylethylene dicarboxylate.
4, 4' Biphenyldiformate Potassium/graphene composite (K) as shown in FIGS. 7a and 7b2BPDC @ GR) and potassium 4, 4' diphenylethylene dicarboxylate/graphene composite (K)2SBDC @ GR) realizes 4, 4' potassium bifluoride (K)2BPDC) or potassium 4, 4' -diphenylethylene dicarboxylate (K)2SBDC) with graphene, and the composite material has a smaller particle size and thus a larger specific surface area.
6. 4,4 ' -biphenyl diformate, 4 ' -diphenylethylene dicarboxylate and 4,4 ' -potassium biphenyl diformate/graphene composite material (K)2BPDC @ GR) and 4, 4'Stilbene potassium dicarboxylate/graphene composite material (K)2SBDC @ GR) as a negative electrode material for potassium ions
(1) 4,4 ' diphenyl diformate, 4 ' diphenyl ethylene dicarboxylic acid salt and 4,4 ' diphenyl potassium diformate/graphene composite material (K)2BPDC @ GR) and potassium 4, 4' diphenylethylene dicarboxylate/graphene composite (K)2SBDC @ GR) are respectively assembled into a potassium ion battery for electrochemical performance test according to the following steps:
4,4 ' diphenyl diformate, 4 ' diphenyl ethylene dicarboxylic acid salt and 4,4 ' diphenyl potassium diformate/graphene composite material (K)2BPDC @ GR) and potassium 4, 4' diphenylethylene dicarboxylate/graphene composite (K)2SBDC @ GR) is respectively dissolved in a mixed solution of EC (ethylene carbonate) and DMC (dimethyl carbonate) according to a volume ratio of 1:1 with carbon black conductive agent (SP) and polyvinylidene fluoride (PVDF) according to a mass ratio of 6:3:1, N-methyl pyrrolidone is used as a solvent to prepare a slurry, the slurry is uniformly coated on a clean Cu foil to prepare an electrode plate which is used as a negative electrode material of a potassium ion battery, a glass fiber membrane is used as a diaphragm, metal potassium is used as a counter electrode, and KFSI (potassium bifluorosulfonyl imide) with an electrolyte of 1mol/L is dissolved in the mixed solution of EC (ethylene carbonate) and DMC (dimethyl carbonate) according to a volume ratio of. Adopting a 2032 type button battery, assembling a half battery in a glove box filled with 99.999% high-purity argon, and testing after assembling.
And (3) testing conditions are as follows: cyclic Voltammetry (CV) curves were tested on an Arbin 2000 electrochemical workstation; the constant temperature charging and discharging curve is tested in a LAND Electronic Co.CT2001A tester at room temperature, and the voltage window is 0.1-2.5V. Electrochemical Impedance Spectroscopy (EIS) test on a Solartron Analytical instrument at 10-2-105Frequency range test in Hz.
As shown in FIG. 8 a-FIG. 15b, 4, 4' -Biphenyldiformate Potassium (K)2BPDC) and graphene composite (K) thereof2BPDC @ GR) are shown in fig. 8a and 8b, from which a pair of distinct redox peaks corresponding to 0.35V and 0.97V (vs.k) can be obtained+K), the reduction peak position is higher relative to potassium terephthalate (0.32V) due to the extended pi conjugation, as shown in fig. 15 a. From 4, 4' -Biphenyldiformate Potassium (K)2BPDC) and graphene in-situ composite material (K) thereof2BPDC @ GR) with different current densitiesThe rate capability test under the degree can observe 4, 4' diphenyl potassium diformate (K)2BPDC) at 50/100/200/500mA g-1Respectively has 105/93/76/52mAh g at current density-1The actual specific capacity of the material has better rate performance, and the figure is 9 a. And 4, 4' potassium bifendate and graphene in-situ composite material (K)2BPDC @ GR) at 100/200/500/1000mA g-1Respectively has 165/143/135/99mAh g at current density-1Has excellent rate capability, see fig. 9 b. Far better than terephthalic acid in rate capability, see fig. 15 b. 4, 4' -Biphenyldiformate Potassium (K)2BPDC) at 20mA g-1The low-cycle 100-week-old lithium ion battery has excellent cycle stability, the capacity retention rate is close to 100 percent, and the average specific capacity is 120mAh g-1，See fig. 10 a. 4, 4' potassium bifendate and graphene in-situ composite material (K) due to high electronic conductivity and hyperconjugate providing larger transmission channel of three-dimensional ions and electrons2BPDC @ GR) at 50mA g-1The average specific capacity of the alloy is 170mAh g after 100 cycles of lower circulation-1，See FIG. 10b, and at 1000mA g-1Has 75mAh g after 3000 weeks of circulation under high current-1Has excellent rate capability, see fig. 10 c.
Wherein, the 4, 4' -diphenylethylene potassium dicarboxylates (K)2SBDC) and graphene in-situ composite material (K) thereof2SBDC @ GR), see fig. 11a and 11b, from which a pair of distinct redox peaks corresponding to 0.55V and 1.12V (vs.k) were obtained+K), the reduction peak position is higher relative to potassium terephthalate (0.32V) due to the extended pi-conjugation, fig. 15 a. From 4, 4' -Diphenylethylene dicarboxylic acid potassium salt (K)2SBDC) and graphene in-situ composite material (K) thereof2SBDC @ GR) under different current densities, and potassium 4, 4' -diphenylethylene dicarboxylate (K) can be observed2SBDC) at 50/100/200/500mA g-1Respectively has 74/55/40/26mAh g at current density-1The actual specific capacity of the material has better rate performance, and the figure is 12 a. And 4, 4' -potassium diphenylethylene dicarboxylate and graphene in-situ composite material (K)2SBDC @ GR) at 100/200/500/1000mA g-1Respectively at a current density ofHas 136/117/98/66mAh g-1Has excellent rate capability, see fig. 12 b. Far better than terephthalic acid in rate capability, see fig. 15 b. 4, 4' -Diphenyl ethylene Potassium dicarboxylates (K)2SBDC) at 20mA g-1The low-cycle 100-week-old lithium ion battery has excellent cycle stability, the capacity retention rate is close to 100 percent, and the average specific capacity is 81mAh g-1See fig. 13 a. 4, 4' -potassium diphenylethylene dicarboxylate and graphene in-situ composite material (K) due to high electronic conductivity and hyperconjugate to provide larger three-dimensional ion and electron transmission channels2SBDC @ GR) at 50mA g-1The average specific capacity of the alloy is 124mAh g after the circulation for 100 weeks-1See fig. 13b, has excellent rate capability.
The SP is used as a conductive additive of a potassium ion negative electrode material, and the contribution of a multiplying power test of the SP to the actual specific capacity under different current densities is shown in figure 14.
Comparative example 1
Lithium terephthalate (Li)2TP) as a negative electrode material, and comprises the following specific steps: lithium terephthalate, SP and PVDF are prepared into slurry by taking N-methyl pyrrolidone as a solvent according to the mass ratio of 6:3:1, the slurry is uniformly coated on a clean Cu foil to prepare an electrode plate which is used as a negative electrode material of a potassium ion battery, a glass fiber membrane is used as a diaphragm, metal potassium is used as a counter electrode, and KFSI with 1mol/L electrolyte is dissolved in a mixed solution of EC and DMC according to the volume ratio of 1: 1. A 2032 type button cell is adopted, and half-cell assembly is carried out in a glove box filled with 99.999 percent high-purity argon.
The obtained battery is subjected to cycle performance test, and cannot show electrochemical activity, compared with organic potassium salt, the organic lithium carboxylate salt as a potassium ion battery negative electrode material cannot show reversible potassium ion deintercalation performance, and due to the fact that the potassium ion radius is large, the molecular structure of lithium terephthalate cannot provide a transmission channel of the lithium terephthalate salt, and electrochemical potassium storage cannot be achieved, and therefore the lithium carboxylate salt cannot be used as a potassium ion secondary battery electrode material.
Comparative example 2
Potassium terephthalate (K)2TP) as a negative electrode material, and the specific steps thereofThe method comprises the following steps: potassium terephthalate, SP and PVDF are prepared into slurry by taking N-methyl pyrrolidone as a solvent according to the mass ratio of 6:3:1, the slurry is uniformly coated on a clean Cu foil to prepare an electrode plate which is used as a negative electrode material of a potassium ion battery, a glass fiber membrane is used as a diaphragm, metal potassium is used as a counter electrode, and KFSI with 1mol/L electrolyte is dissolved in a mixed solution of EC and DMC according to the volume ratio of 1: 1. A 2032 type button cell is adopted, and half-cell assembly is carried out in a glove box filled with 99.999 percent high-purity argon.
The obtained battery is subjected to cyclic performance test, the reversible Cyclic Voltammetry (CV) curve graph is shown in figure 15a, the cyclic performance is shown in figure 15b, and as can be seen from figure 15, the potassium ion battery shows a relatively obvious charge and discharge platform, but the discharge and charge platform is located at 0.32/0.83V due to low pi conjugation, and the reduction potential is low; and its rate capability is poor due to its low three-dimensional ion and electron transport channels.
The data for specific comparison of examples and comparative examples are given in the following table:
to sum up, 4' -Biphenyldiformate Potassium (K)2BPDC) and graphene composite (K) thereof2BPDC @ GR) and potassium 4, 4' diphenylethylene dicarboxylate (K)2SBDC) and graphene composite material (K) thereof2SPDC @ GR) as a new family of potassium ion batteries, has higher reduction potential in the potassium ion batteries due to a super pi conjugated structure; the super pi conjugated structure can provide a larger potassium ion and electron three-dimensional transmission channel and can realize excellent rate capability; and has excellent practical specific capacity and cycling stability. The organic potassium ion battery has very important significance as a new family of organic potassium ion batteries.
The technical means of the present invention can be preferably realized according to the description of the present specification.
Claims (3)
- Use of a 4,4 'bifendate/graphene composite or a 4, 4' diphenylethylene dicarboxylate/graphene composite as a potassium ion battery negative electrode material, characterized in that when the 4,4 'bifendate/graphene composite is used as a potassium ion battery negative electrode material, the 4, 4' bifendate/graphene composite is obtained by the following method steps, comprising the steps of:A. preparing a series of solutions: weighing a plurality of parts of 4, 4' -biphenyl diformate with different masses, and preparing a plurality of series standard solutions with sequentially increasing concentrations by using deionized water;B. selecting a standard solution: dropwise adding all the series of standard solutions into absolute ethyl alcohol or N-methyl pyrrolidone respectively, wherein the volume ratio of the standard solutions to the absolute ethyl alcohol or the N-methyl pyrrolidone is 1:10, and selecting the series of standard solutions which can just enable the absolute ethyl alcohol or the N-methyl pyrrolidone to generate precipitation from all the series of standard solutions to obtain a standard solution, wherein the concentration of the standard solution is S mg/L;C. determining the concentration of the reaction solution, the dosage of absolute ethyl alcohol or N-methyl pyrrolidone and the dosage of graphene: preparing a reaction solution with the concentration of X mL being higher than that of a standard solution, wherein the concentration of the reaction solution is F mg/mL; the amount of graphene used (mg) ═ X (F-S) × 0.05; determining the dosage of the absolute ethyl alcohol or the N-methyl pyrrolidone according to the volume ratio of the reaction solution to the absolute ethyl alcohol or the N-methyl pyrrolidone being 1: 10;d, preparing a 4, 4' -biphenyl diformate/graphene composite material:(1) uniformly stirring graphene and absolute ethyl alcohol or N-methyl pyrrolidone to obtain a uniform mixed solution;(2) dropwise adding a reaction solution into the mixed solution under a stirring state to obtain a suspension;(3) stirring the turbid liquid, carrying out solid-liquid separation, washing and drying to obtain a 4, 4' biphenyl diformate/graphene composite material;when the 4,4 'diphenyl ethylene dicarboxylate/graphene composite material is used as a potassium ion battery cathode material, the 4, 4' diphenyl ethylene dicarboxylate/graphene composite material is obtained by the following method steps, including the following steps:A. preparing a series of solutions: weighing a plurality of parts of 4, 4' -diphenylethylene dicarboxylate with different masses, and preparing a plurality of series standard solutions with sequentially increasing concentrations by using deionized water;B. selecting a standard solution: dropwise adding all the series of standard solutions into absolute ethyl alcohol or N-methyl pyrrolidone respectively, wherein the volume ratio of the standard solutions to the absolute ethyl alcohol or the N-methyl pyrrolidone is 1:10, and selecting the series of standard solutions which can just enable the absolute ethyl alcohol or the N-methyl pyrrolidone to generate precipitation from all the series of standard solutions to obtain a standard solution, wherein the concentration of the standard solution is S mg/L;C. determining the concentration of the reaction solution, the dosage of absolute ethyl alcohol or N-methyl pyrrolidone and the dosage of graphene: preparing a reaction solution with the concentration of X mL being higher than that of a standard solution, wherein the concentration of the reaction solution is F mg/mL; the amount of graphene used (mg) ═ X (F-S) × 0.05; determining the dosage of the absolute ethyl alcohol or the N-methyl pyrrolidone according to the volume ratio of the reaction solution to the absolute ethyl alcohol or the N-methyl pyrrolidone being 1: 10;d, preparing a 4, 4' diphenyl ethylene dicarboxylate/graphene composite material:(1) uniformly stirring graphene and absolute ethyl alcohol or N-methyl pyrrolidone to obtain a uniform mixed solution;(2) dropwise adding a reaction solution into the mixed solution under a stirring state to obtain a suspension;(3) and stirring the turbid liquid, carrying out solid-liquid separation, washing and drying to obtain the 4, 4' diphenylethylene dicarboxylate/graphene composite material.
- 2. The use of the 4,4 ' biphenyldicarboxylate/graphene composite material or the 4,4 ' diphenylethylene dicarboxylate/graphene composite material according to claim 1 as a potassium ion battery negative electrode material, wherein, when the 4,4 ' biphenyldicarboxylate/graphene composite material is used as a potassium ion battery negative electrode material, the concentrations of the several sequentially increasing concentration series of standard solutions in step a are 2mg/mL, 3mg/mL, 5mg/mL, 10mg/mL and 20mg/mL, respectively; all stirring in the step D adopts ultrasonic stirring, and the time of all ultrasonic stirring is 2-4 h; and D, performing suction filtration or centrifugation as solid-liquid separation in the step (3) in the step D, wherein the washing is washing by adopting absolute ethyl alcohol, the drying is vacuum drying, the vacuum drying time is 12-24h, and the temperature is 80-120 ℃.
- 3. The use of the 4,4 ' biphenyldicarboxylate/graphene composite material or the 4,4 ' stilbene dicarboxylate/graphene composite material according to claim 1 as a negative electrode material for potassium ion batteries, wherein, when the 4,4 ' stilbene dicarboxylate/graphene composite material is used as a negative electrode material for potassium ion batteries, the concentrations of the several sequentially increasing series of standard solutions in step a are 2mg/mL, 3mg/mL, 5mg/mL, 10mg/mL and 20mg/mL, respectively; all stirring in the step D adopts ultrasonic stirring, and the time of all ultrasonic stirring is 2-4 h; and D, performing suction filtration or centrifugation as solid-liquid separation in the step (3) in the step D, wherein the washing is washing by adopting absolute ethyl alcohol, the drying is vacuum drying, the vacuum drying time is 12-24h, and the temperature is 80-120 ℃.
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