CN114843473B - Composite slurry applied to iron lithium battery and preparation method thereof - Google Patents
Composite slurry applied to iron lithium battery and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000002002 slurry Substances 0.000 title claims abstract description 42
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000006258 conductive agent Substances 0.000 claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 24
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 23
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 16
- 239000006229 carbon black Substances 0.000 claims abstract description 10
- 229920000767 polyaniline Polymers 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 6
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 6
- 239000003049 inorganic solvent Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000005518 polymer electrolyte Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 238000007500 overflow downdraw method Methods 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims description 3
- 229910010941 LiFSI Inorganic materials 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses composite slurry applied to an iron-lithium battery, which comprises an anode composite material, a high-solid-content conductive agent and a solid electrolyte, wherein the anode composite material is a net-shaped structure composite material formed by grapheme/carbon nano tube/lithium iron phosphate@PANI through structural design, and the high-solid-content conductive agent is a composite material formed by combining carbon black, CNT and grapheme into a dot-line-surface combination. According to the graphene/carbon nanotube/lithium iron phosphate@pani composite material, a reticular porous structure is formed, and the carbon nanotube has excellent conductivity, so that the conductivity of the positive electrode material is improved.
Description
Technical Field
The invention relates to the technical field of lithium iron batteries, in particular to composite slurry applied to a lithium iron battery and a preparation method thereof.
Background
In the working process of the lithium ion battery, oxygen release by the reconstruction of the surface of the positive electrode in a delithiated state can occur at the electrode/electrolyte interface, electrolyte decomposition, and formation and decomposition of a solid electrolyte intermediate layer (SEI) can all lead to gas production. And the gas production can lead to the expansion, deformation, thermal runaway and other safety disasters of the battery, thereby causing serious threat to the safety performance of the lithium ion battery. In recent years, reports on lithium ion battery safety disasters are endless, and especially in the case of increasing energy density, safety problems become prominent. How to further increase the energy density on the basis of ensuring good safety is important to improve the competitiveness of the lithium ion battery in various energy storage devices.
In the electrode material of the lithium ion battery, the conductive agent provides an electron movement channel, so that the electron conductivity of the electrode material is increased, and the electrode is ensured to have good charge and discharge performance. Solid state lithium batteries are considered as a reliable option to substantially improve the safety of lithium batteries by employing nonflammable solid electrolytes instead of organic liquid electrolytes. The solid electrolyte is matched with the high-efficiency conductive agent to ensure the interface stability of the anode material and the cathode material in the cyclic process, and is matched with the metal lithium anode with high energy density to realize higher energy density, so that the safety performance, the multiplying power performance and the cyclic performance of the conventional lithium ion battery are low.
Disclosure of Invention
The invention aims to provide composite slurry applied to an iron-lithium battery and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the composite slurry applied to the iron lithium battery comprises a positive electrode composite material, a high-solid-content conductive agent and a solid electrolyte, wherein the positive electrode composite material is a net-shaped structure composite material formed by grapheme/carbon nano tube/lithium iron phosphate@pani through structural design, and the high-solid-content conductive agent is a composite material combined by comprehensively forming carbon black, CNT and grapheme into a dot line and a plane.
Preferably, the solid electrolyte is one or more of an Inorganic Solid Electrolyte (ISE), a Solid Polymer Electrolyte (SPE) and a Composite Polymer Electrolyte (CPE).
The invention also provides a preparation method of the composite slurry applied to the iron-lithium battery, which is characterized by comprising the following steps:
Step one: mixing lithium iron phosphate, graphene and carbon nanotubes according to a certain mass ratio, uniformly mixing the three materials by using a mechanical fusion method, and heating the mixture at 120-150 ℃ for 3-5h under vacuum to form a mixed material.
Step two: placing the mixed material into ethanol, mixing by ultrasonic treatment to uniformly disperse the mixed material, adding HCl solution with a certain concentration and aniline for mixing, adding HCl and (NH 4)2S2O8 mixed solution with a certain concentration, controlling the temperature by using an ice-water bath, stirring for 12-15h, centrifuging the obtained mixed solution, and vacuum drying at 60 ℃ for 12-15h to obtain the graphene/carbon nano tube/lithium iron phosphate@pani composite material;
Step three: mixing a conductive substance and a solvent, magnetically stirring at 200-600rpm for 2-3h, performing ultrasonic treatment for 0.5-1h, dispersing the conductive substance, adding a dispersing agent into the solution, and performing ultrasonic treatment for 1-1.5h to obtain high-solid-content conductive agent slurry;
step four: PEO and a binder in a certain mass ratio are dissolved in NMP to prepare a binder solution, and then lithium salt is added. Preparing a graphene/carbon nano tube/lithium iron phosphate@pani composite material, high-solid-content conductive agent slurry and adhesive solution into slurry according to a certain mass ratio, and uniformly mixing in an agate mortar to obtain the composite slurry.
Preferably, the conductive material in the high-solid-content conductive agent slurry is 15-20%, the dispersing agent is 0.1-5%, and the solvent is 75-85%.
Preferably, the high-solid-content conductive agent comprises 40-50% of CNT,8-10% of graphene and 40-50% of carbon black.
Preferably, the dispersing agent is selected from one or more of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol.
Preferably, the solvent comprises an organic solvent and an inorganic solvent, wherein the organic solvent is one or two of N, N-dimethylformamide and N, N-dimethylacetamide, and the inorganic solvent is water.
Preferably, the binder is one or more of PTFE, PVDF, CMC, GA, CG and XG.
Preferably, the lithium salt is one or more of LiFP 6、LiBF4、LiBOB、LiTFSI、LiFSI、LiDFOB、LiClO4、LiAsO4.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a graphene/carbon nano tube/lithium iron phosphate@PANI composite material, which forms a reticular porous structure, has excellent conductivity of a carbon nano tube, improves the conductivity of a positive electrode material, and has a pinning effect on positive electrode material ions by a PANI layer, thereby improving the utilization rate of active substances, and improving the cycle stability and coulomb efficiency of the composite material.
(2) The invention provides a high-solid-content conductive agent, wherein the solid content exceeds 5% of the total mass fraction, CNT, graphene and carbon black are adopted for the first time, perfect combination of points, lines and surfaces is formed, the conductivity is effectively improved, the compaction performance can be effectively improved when the conductive agent is used as a conductive agent of a lithium battery, and the multiplying power performance and the cycle performance of the battery are improved.
(3) The invention provides an all-solid-state battery and a preparation method thereof, wherein a solid electrolyte containing a high-solid-content conductive agent has better interface stability with a composite positive electrode material, and in the circulation process, the excellent circulation stability is maintained, and the circulation performance of the all-solid-state battery is improved.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The composite slurry applied to the iron-lithium battery comprises a positive electrode composite material, a high-solid-content conductive agent and a solid electrolyte, wherein the positive electrode composite material is a net-shaped structure composite material formed by graphene/carbon nano tube/lithium iron phosphate@PANI through structural design, and the high-solid-content conductive agent is a composite material formed by combining carbon black, CNT and graphene into a dot-line-surface combination.
The solid electrolyte of this embodiment is one or more of an Inorganic Solid Electrolyte (ISE), a Solid Polymer Electrolyte (SPE) and a Composite Polymer Electrolyte (CPE).
The invention also provides a preparation method of the composite slurry applied to the iron-lithium battery, which is characterized by comprising the following steps:
Step one: mixing lithium iron phosphate, graphene and carbon nanotubes according to a certain mass ratio, uniformly mixing the three materials by using a mechanical fusion method, and heating the mixture at 120-150 ℃ for 3-5h under vacuum to form a mixed material.
Step two: placing the mixed material into ethanol, mixing by ultrasonic treatment to uniformly disperse the mixed material, adding HCl solution with a certain concentration and aniline for mixing, adding HCl and (NH 4)2S2O8 mixed solution with a certain concentration, controlling the temperature by using an ice-water bath, stirring for 12-15h, centrifuging the obtained mixed solution, and vacuum drying at 60 ℃ for 12-15h to obtain the graphene/carbon nano tube/lithium iron phosphate@pani composite material;
Step three: mixing a conductive substance and a solvent, magnetically stirring at 200-600rpm for 2-3h, performing ultrasonic treatment for 0.5-1h, dispersing the conductive substance, adding a dispersing agent into the solution, and performing ultrasonic treatment for 1-1.5h to obtain high-solid-content conductive agent slurry;
step four: PEO and a binder in a certain mass ratio are dissolved in NMP to prepare a binder solution, and then lithium salt is added. Preparing a graphene/carbon nano tube/lithium iron phosphate@pani composite material, high-solid-content conductive agent slurry and adhesive solution into slurry according to a certain mass ratio, and uniformly mixing in an agate mortar to obtain the composite slurry.
The conductive material in the high-solid-content conductive agent slurry of the embodiment is 15-20%, the dispersing agent is 0.1-5% and the solvent is 75-85%.
In the high-solid-content conductive agent of the embodiment, 40-50% of CNT,8-10% of graphene and 40-50% of carbon black are mixed.
The dispersing agent of the present embodiment is selected from one or more of polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.
The solvent of this embodiment includes an organic solvent and an inorganic solvent, wherein the organic solvent is one or two of N, N-dimethylformamide and N, N-dimethylacetamide, and the inorganic solvent is water.
The binder of this embodiment is one or more of PTFE, PVDF, CMC, GA, CG and XG.
The lithium salt of this embodiment is one or more of lifps 6、LiBF4、LiBOB、LiTFSI、LiFSI、LiDFOB、LiClO4、LiAsO4.
Example 1
A preparation method of composite slurry applied to an iron lithium battery comprises the following steps:
(1) Mixing 30g of lithium iron phosphate, 15g of graphene and 5g of carbon nano tube by a mechanical method, uniformly mixing the three by a mechanical fusion method, and heating the mixture at 120-150 ℃ for 3-5h under vacuum to form a mixed material;
(2) Placing the mixed material into 50ml of ethanol, mixing through ultrasonic treatment to enable the mixed material to be dispersed uniformly, adding 2.5g of 15ml of 2M HCl solution to mix with aniline, adding 5g of 15ml of 2M HCl and (NH 4)2S2O8 mixed solution), controlling the temperature through an ice-water bath, stirring for 12-15h, centrifuging the obtained mixed solution, and drying in vacuum at 60 ℃ for 12-15h to obtain the graphene/carbon nano tube/lithium iron phosphate@pani composite material;
(3) Uniformly mixing 45% of CNT, 10% of graphene and 45% of carbon black by a mechanical method to form a conductive substance, mixing the conductive substance with a solvent, magnetically stirring at 400rpm for 2-3 hours, performing ultrasonic treatment for 0.5-1 hour, dispersing the conductive substance, adding a dispersing agent into the solution, and performing ultrasonic treatment for 1-1.5 hours to obtain the conductive agent slurry with high solid content.
(4) PEO and a binder in a mass ratio of 2:1 were dissolved in NMP to prepare a binder solution, followed by the addition of a lithium salt. The graphene/carbon nano tube/lithium iron phosphate@pani composite material, high-solid-content conductive agent slurry and adhesive solution are prepared into slurry according to the mass ratio of 75:10:15, and the slurry is uniformly mixed in an agate mortar to obtain the composite slurry.
Example 2
Example 2 was prepared according to the method of example 1, except that in step (2), the mixed material was placed in 50ml of ethanol, and mixed by ultrasonic treatment to uniformly disperse it, then 5g of 15ml of 2m HCl solution was added and mixed with aniline, then 10g of 15ml of 2m HCl and (NH 4)2S2O8 mixed solution) were added, and the temperature was controlled by ice-water bath and stirred for 12-15 hours, and the obtained mixed solution was centrifuged and dried under vacuum at 60 ℃ for 12-15 hours to obtain a graphene/carbon nanotube/lithium iron phosphate@pani composite material.
Example 3
Example 3 was prepared according to the method of example 1, except that in step (2), the mixed material was placed in 50ml of ethanol, and mixed by ultrasonic treatment to uniformly disperse it, then 10g of 15ml of 2m HCl solution was added to mix with aniline, then 20g of 15ml of 2m HCl and (NH 4)2S2O8 mixed solution was added, and the temperature was controlled by ice-water bath to stir for 12-15 hours, and the obtained mixed solution was centrifuged and dried under vacuum at 60 ℃ for 12-15 hours to obtain a graphene/carbon nanotube/lithium iron phosphate@pani composite material.
Comparative example 1
Comparative example 1 was prepared as in example 1, except that steps (1) and (2) were not required, and a lithium iron phosphate cathode material was used instead of the graphene/carbon nanotube/lithium iron phosphate @ PANI composite.
Comparative example 2
Comparative example 2 was prepared in the same manner as in example 1 except that step (3) was not required, and a carbon black conductive agent was used instead of the high solid content conductive agent slurry.
Comparative example 3
Comparative example 3 was prepared in the same manner as in example 1 except that in step (4), an electrolyte of EC: emc=3:7 was used instead of the solid electrolyte.
(1) Cycle test
The batteries of examples 1 to 3 and comparative examples 1 to 3 were charged to 3.65V with a constant current and constant voltage of 1C at 25 ℃ and the off-current was 0.05C, respectively, and then the battery 1C was discharged to 2.0V with a constant current, and the discharge capacity Q0 was recorded, which is the cycle first discharge capacity. This is a complete cycle, and the battery is cycled 500, 1000 weeks in this way, and the discharge capacities Q500, Q1000 for cycles 500, 1000 weeks are recorded. Wherein 1000-week cyclic capacity retention = q1000/q0 x 100%.
(2) High temperature shelf test
The batteries of examples 1 to 3 and comparative examples 1 to 3 were charged to 3.65V at 25℃with a constant current and a constant voltage of 1C, respectively, and the cut-off current was 0.05C, and then the battery volume was measured by a drainage method and recorded as V0. The fully charged cells were then transferred to a 60 ℃ incubator and stored for 28 days. After 28 days of storage, the battery was taken out, and the volume of the battery after storage was again measured by a drainage method and recorded as V28. Wherein, the volume expansion rate is stored for 60 ℃ for 28 days= (V28-V0)/V0 for 100%.
The batteries of examples 1 to 3 and comparative examples 1 to 3 were charged to 3.65V at a constant current and a constant voltage at 25℃with a cut-off current of 0.05C, respectively, and then the battery 1C was discharged to 2.0V with a constant current, and the discharge capacity Q0 was recorded. The fully charged cells were then transferred to a 60 ℃ incubator and stored for 28 days. After 28 days of storage, the battery was taken out, and again 1C was discharged to 2.0V at constant current, and the discharge capacity Q28 was recorded. Wherein capacity retention = Q28/Q0 is 100%.
TABLE 1
From the results of the experimental tests, it can be seen from examples 1 to 3 that as the mass fraction of aniline increases, it is helpful to form a more stable network structure, which exhibits a better retention of the cyclic capacity in terms of battery performance, but when the aniline content exceeds a certain amount, the presence alone in the positive electrode material hinders ion transport, thereby affecting battery performance.
The results of the experimental tests were combined, and in example 1 and comparative examples 1 to 3, the composite slurry of the present invention exhibited more excellent properties. This is mainly due to the stable network structure formed by the positive electrode composite material and the improvement of the performance of the composite conductive paste, and when the composite conductive paste is used as a solid-state battery positive electrode material, the composite conductive paste is synergistic, so that the composite conductive paste has excellent performance.
In combination, the composite slurry can greatly improve the performance of the iron-lithium battery, wherein the solid electrolyte can also better solve the problems of gas production and the like of the high-temperature battery, and still has excellent capacity retention rate and cycle performance at high temperature.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. The composite slurry applied to the iron lithium battery is characterized by comprising a positive electrode composite material, a high-solid-content conductive agent and a solid electrolyte, wherein the positive electrode composite material is a net-shaped structure composite material formed by grapheme/carbon nano tube/lithium iron phosphate@PANI through structural design, and the high-solid-content conductive agent is a composite material formed by combining carbon black, CNT and grapheme into a dot-line-surface combination;
the preparation method of the composite slurry comprises the following steps:
Step one: mixing lithium iron phosphate, graphene and carbon nanotubes according to a certain mass ratio, uniformly mixing the three materials by using a mechanical fusion method, and heating the mixture at 120-150 ℃ for 3-5h under vacuum to form a mixed material;
step two: placing the mixed material into ethanol, mixing by ultrasonic treatment to uniformly disperse the mixed material, adding HCl solution with a certain concentration and aniline for mixing, adding HCl and (NH 4)2S2O8 mixed solution with a certain concentration, controlling the temperature by using an ice-water bath, stirring for 12-15h, centrifuging the obtained mixed solution, and vacuum drying at 60 ℃ for 12-15h to obtain the graphene/carbon nano tube/lithium iron phosphate@pani composite material;
Step three: mixing a conductive substance and a solvent, magnetically stirring at 200-600rpm for 2-3h, performing ultrasonic treatment for 0.5-1h, dispersing the conductive substance, adding a dispersing agent into the solution, and performing ultrasonic treatment for 1-1.5h to obtain high-solid-content conductive agent slurry;
step four: dissolving PEO and a binder in a certain mass ratio in NMP to prepare a binder solution, and then adding lithium salt; preparing a graphene/carbon nano tube/lithium iron phosphate@pani composite material, high-solid-content conductive agent slurry and adhesive solution into slurry according to a certain mass ratio, and uniformly mixing in an agate mortar to obtain the composite slurry.
2. The composite slurry for use in an iron lithium battery according to claim 1, wherein the solid electrolyte is one or more of an Inorganic Solid Electrolyte (ISE), a Solid Polymer Electrolyte (SPE) and a Composite Polymer Electrolyte (CPE).
3. The composite slurry for an iron-lithium battery according to claim 1, wherein the conductive material in the high-solid-content conductive agent slurry is 15-20%, the dispersant is 0.1-5% and the solvent is 75-85%.
4. The composite slurry applied to the iron-lithium battery according to claim 1, wherein the high-solid-content conductive agent comprises 40-50% of CNT,8-10% of graphene and 40-50% of carbon black.
5. A composite slurry for use in a lithium iron battery according to claim 3, wherein the dispersant is selected from one or more of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol.
6. The composite slurry for use in an iron lithium battery according to claim 3, wherein the solvent comprises an organic solvent and an inorganic solvent, the organic solvent is one or two of N, N-dimethylformamide and N, N-dimethylacetamide, and the inorganic solvent is water.
7. The composite slurry for use in an iron lithium battery according to claim 1, wherein the binder is one or more of PTFE, PVDF, CMC, GA, CG and XG.
8. The composite slurry process for use in an iron lithium battery of claim 1, wherein the lithium salt is one or more of LiFP 6、LiBF4、LiBOB、LiTFSI、LiFSI、LiDFOB、LiClO4、LiAsO4.
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