CN117810571A - Preparation method and application of a carbon nitride catalyzed PP-based high-efficiency lithium supplement separator - Google Patents
Preparation method and application of a carbon nitride catalyzed PP-based high-efficiency lithium supplement separator Download PDFInfo
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Abstract
The invention relates to the technical field of lithium battery materials, in particular to a preparation method and application of a carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm. By adopting the technical scheme, the lithium supplementing modification layer on the diaphragm shows a rapid and accurate lithium releasing effect, and the practical application problem of some high-decomposition voltage lithium supplementing reagents is solved. The lithium-supplementing material has application universality in battery manufacturing, and can realize the lithium supplementing requirements of various lithium-deficient electrodes.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a preparation method and application of a carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm.
Background
In recent years, under the double anxiety of energy source problems and environmental problems, lithium ion batteries with excellent performance characteristics such as high energy density, high open-circuit voltage, long cycle life and the like are vigorously developed at application ends of consumer electronics, power batteries, energy storage power stations and the like. The current lithium ion battery system also causes lower energy density due to unavoidable lithium capacity attenuation problem in the circulation process, so that in order to have a battery core with higher energy density, enough lithium storage library is required to be introduced into the system while the battery manufacturing process is not influenced, the life of long-acting stable circulation of lithium ions is promoted, and the battery core with high energy density is updated.
The lithium-supplementing strategy widely used at present mostly adopts lithium-rich reagents (such as Li 6 CoO 4 , Li 3 P, liF, li2O, etc.) are added to the electrode for lithiation, but the additional addition of these agents can affect the uniformity of the slurry and even cause gelation. And the lithium supplementing reagent can be decomposed into a plurality of gases or inert substances which remain in the electrode in the circulating process, so that the subsequent battery performance is affected. Unlike the conventional lithium supplementing strategy, the lithium supplementing diaphragm maintains the stability of the battery while realizing the lithium supplementing effect, but the application of the lithium supplementing diaphragm is still limited by the slow release rate of lithium, so far, the research is carried out for the problem. The realization of low-cost and high-efficiency lithium supplementation of the lithium supplementation diaphragm through a catalytic strategy is also a key problem for the further development of lithium ion batteries.
Disclosure of Invention
The inventionThe preparation method and the application of the carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm are provided, the PP-based lithium supplementing diaphragm with the rapid lithium supplementing rate is prepared, meanwhile, a composite catalyst with a two-dimensional lamination configuration is designed, and the high added value of waste graphite is developed; and PP-based high-efficiency lithium supplementing diaphragm and graphite phase carbon nitride g-C 3 N 4 The modified copper foil is matched with a lithium iron phosphate positive electrode material, lithium ions consumed at the positive electrode end are compensated by using an electrochemical in-situ lithium supplementing technology, and an SEI film is pre-established at the negative electrode end, so that the cathode-free lithium ion battery with excellent cycle stability and high energy density is constructed.
In order to achieve the above purpose, the invention provides a preparation method of a carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm, which comprises the following steps:
s1: pretreating waste graphite and mechanically shearing and stripping to obtain a thin-layer graphene nano sheet;
s2: c, the thin-layer graphene nano sheet obtained in the step S1 and graphite phase carbon nitride g-C 3 N 4 Performing electrostatic self-assembly to obtain a composite catalyst with a two-dimensional lamination structure;
s3: composite catalyst obtained by S2 and lithium oxalate Li 2 C 2 O 4 Mixing with a first binder, and sequentially carrying out coarse grinding and fine grinding to obtain ground powder;
s4: mixing the ground powder obtained in the step S3 with a first organic solvent, and then sequentially carrying out first stirring and first defoaming stirring to obtain slurry;
s5: coating the slurry obtained in the step S4 on the surface of a PP base film to form a lithium supplementing interface layer; after the coating is completed, the coated product is subjected to first vacuum drying to obtain g-C 3 N 4 Catalytic PP-based high-efficiency lithium supplementing diaphragm.
Preferably, the waste graphite in S1 is obtained by recycling the negative electrode of the waste lithium ion battery, and the method comprises the following steps: discharging the waste lithium ion battery in sodium chloride solution, and then sequentially carrying out disassembly, crushing, screening and calcination to obtain waste graphite powder;
the method for disassembling, crushing and screening is not particularly limited, the method is realized by adopting the technical scheme well known in the art, the calcining temperature is 500-800 ℃, and the residual organic components such as adhesive, electrolyte and the like in the waste graphite are removed by calcining, so that the thin-layer graphite sheet with high purity and better performance is obtained.
And the mechanical stripping is to strip the obtained waste graphite powder in a water/dispersant mixed solvent system through mechanical shearing force of a homogenizer to obtain the thin-layer graphene nano sheet.
Preferably, the electrostatic self-assembly in S2 is realized by carrying out ultrasonic stripping on graphene nano-sheets and graphite phase carbon nitride g-C in a water/ethanol mixed solvent 3 N 4 Electrostatic self-assembly is carried out to obtain the composite catalyst SGr/g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the Thin graphene nanoplatelets and graphite phase carbon nitride g-C 3 N 4 The mass ratio of (1-2): 1.
preferably, the first binder in S3 is at least one of polyvinylidene fluoride, polyvinyl acetate, and polyvinylidene chloride-hexafluoropropylene copolymer.
Preferably, the composite catalyst in S3 is lithium oxalate Li 2 C 2 O 4 And the mass ratio of the first binder is 2-5: 3-7: 1, a step of; more preferably, the composite catalyst, lithium oxalate Li 2 C 2 O 4 And the mass ratio of the first binder is 2-4: 5-7: 1, a step of; the mass ratio of the composite catalyst to the lithium oxalate to the first binder is controlled in the range, so that the conductivity of the lithium-supplementing reagent lithium oxalate and graphite-phase carbon nitride is improved by introducing the thin graphene nano sheet with high conductivity and large specific surface area; meanwhile, the defect-rich structure in the thin-layer graphene nano sheet can also cooperate with the electrocatalytic effect of ink phase carbon nitride to accelerate the local electron transfer of lithium oxalate, thereby promoting the lithium supplementing reagent to release active Li + And further optimized by control of the comparative example to achieve g-C 3 N 4 Accurate quick lithium compensation of PP base high-efficiency lithium compensation diaphragm of catalysis.
Preferably, the mode of coarse grinding in S3 is not particularly limited, and a method well known in the art is adopted, and the fine grinding mode is preferably to grind in a ball mill for 12-18 hours at a speed of 400-600 r/min.
Preferably, the first organic solvent in S4 is preferably N-methylpyrrolidone.
Preferably, the rotation speed of the first stirring in the step S4 is 500-1000 r/min, and the time of the first stirring is 11-14 h, more preferably 12-13 h.
Preferably, the time of the first deaeration stirring in S4 is preferably 30 min.
The invention removes bubbles in the slurry through the first defoaming stirring, is beneficial to uniformly coating the subsequent slurry on the surface of the PP base film, avoids forming bubbles, prevents cracking or non-uniformity of a subsequent lithium supplementing interface layer, and obtains g-C with good comprehensive performance 3 N 4 Catalytic PP-based high-efficiency lithium supplementing diaphragm.
Preferably, the coating mode in the step S5 is ultrasonic spraying, and the ultrasonic spraying equipment is ultrasonic film spraying equipment; the ultrasonic spraying mode is preferably cross spraying.
Preferably, the flow rate of ultrasonic spraying in the S5 is 0.2-1.0 mL/min, more preferably 0.4-0.6 mL/min; the ultrasonic spraying speed is 10000-15000 mm/min; more preferably 15000 mm/min. According to the invention, the slurry is uniformly coated on the surface of the PP base film by ultrasonic spraying, so that cracks or non-uniformity of a lithium supplementing interface layer is prevented, and g-C with good comprehensive performance is obtained 3 N 4 Catalytic PP-based high-efficiency lithium supplementing diaphragm.
The thickness of the lithium-supplementing interface layer is 5-12 μm, more preferably 5-10 μm. The thickness of the lithium-supplementing interfacial layer is controlled in the range, so that the balance between the capacity of the high-lithium-supplementing surface and the lithium ion release kinetics is achieved while the thin-layer lithium-supplementing diaphragm is uniformly coated.
Preferably, the temperature of the first vacuum drying in the step S5 is preferably 55-80 ℃, more preferably 60 ℃; the time for the first vacuum drying is preferably 10 to 15 hours, more preferably 11 to 13 hours. The present invention removes the solvent component remaining in the separator by the first vacuum drying.
Preferably, g-C in S5 3 N 4 The thickness of the catalyzed PP-based high-performance lithium supplementing separator is preferably 15-22 mu m, more preferably 15-20 mu m.
The method provided by the invention can be used for preparing the rapid and accurate nitrogenCarbon-conversion catalyzed PP-based high-efficiency lithium-supplementing separator (SGr/g-C 3 N 4 LCO), a high added value of waste graphite was developed by designing a composite catalyst with a two-dimensional lamination configuration; and the PP-based high-efficiency lithium supplementing diaphragm and graphite phase carbon nitride g-C are utilized 3 N 4 The modified copper foil is matched with a lithium iron phosphate positive electrode material, so that the cathode-free lithium ion battery with high energy density is constructed.
g-C prepared by preparation method of carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm 3 N 4 The application of the catalytic PP-based high-efficiency lithium supplementing diaphragm is applied to a non-negative electrode lithium ion battery.
Preferably, the preparation of the non-negative electrode lithium ion battery comprises the following steps:
step one, the bulk graphite phase carbon nitride g-C 3 N 4 Mechanical shearing stripping is carried out to obtain the thin-layer graphite phase carbon nitride g-C 3 N 4 A nanosheet;
step two, the thin layer graphite phase carbon nitride g-C obtained in the step one 3 N 4 Mixing the nanosheets, the second binder and the second organic solvent, and then performing second defoaming stirring to obtain mixed slurry;
thirdly, ultrasonically spraying the mixed slurry obtained in the second step on the surface of the copper foil to form a lithium regulating layer; after the ultrasonic spraying is finished, carrying out second vacuum drying on the ultrasonic-sprayed copper foil to obtain a modified copper foil;
step four, lithium iron phosphate and g-C 3 N 4 The catalyzed PP-based high-efficiency lithium supplementing diaphragm and the modified copper foil obtained in the step three are respectively used as a positive electrode, a diaphragm and a negative electrode, LS-002 is used as electrolyte, and the cathode-free lithium ion battery is constructed.
Preferably, the mechanical exfoliation in the first step is performed by mechanically shearing the bulk graphite phase carbon nitride (g-C) in a water/ethanol mixed solvent by a homogenizer 3 N 4 ) Stripping to obtain thin layer graphite phase carbon nitride (g-C) 3 N 4 ) A nano-sheet.
Preferably, in the second step, the second binder is at least one of sodium carboxymethyl cellulose, styrene-butadiene rubber emulsion and polyethylene binder, and the second organic solvent is N-methyl pyrrolidone.
Preferably, in the second step, the lamellar graphite phase carbon nitride g-C 3 N 4 The mass ratio of the nano sheet to the second binder is 7-12:1. More preferably 8 to 10:1. The invention controls the carbon nitride g-C of the thin-layer graphite phase 3 N 4 And the second binder in the above range by introducing the graphite-phase carbon nitride g-C rich in electronegative N element 3 N 4 To pre-incorporate solvated Li + Li-N bond is formed before deposition to achieve the effect of uniform lithium ion flow, and lithium uniform deposition of the modified copper foil is achieved through regulation and optimization of comparative examples.
Preferably, the second defoaming stirring time in the second step is 30 min. According to the invention, bubbles in the mixed slurry are removed through the second defoaming stirring, so that the subsequent uniform coating of the mixed slurry on the surface of the copper foil is facilitated, the formation of bubbles is avoided, the occurrence of cracks or non-uniformity of a modification layer is prevented, and the modified copper foil with good comprehensive performance is obtained.
Preferably, the ultrasonic spraying equipment in the third step is ultrasonic film spraying equipment; the ultrasonic spraying mode is cross spraying. In the invention, the flow rate of ultrasonic spraying is preferably 0.3-0.8 mL/min, more preferably 0.4-0.6 mL/min; the speed of ultrasonic spraying is preferably 14000-16000 mm/min, more preferably 16000-mm/min. According to the invention, the mixed slurry is uniformly coated on the surface of the copper foil through ultrasonic spraying, so that cracks or non-uniformity of the repair modification layer is prevented, and the modified copper foil with good comprehensive performance is obtained.
Preferably, the temperature of the second vacuum drying is 75-95 ℃, more preferably 80 ℃; the second vacuum drying time is 10 to 15 hours, more preferably 11 to 13 hours. The present invention removes the residual solvent by a second vacuum drying.
Preferably, the thickness of the lithium regulating layer in the third step is 2.5 to 5 μm, more preferably 3 to 5 μm. The present invention controls the thickness of the modified layer in the above range to achieve a balance between Li flux adjustment and energy density while uniformly coating the thin modified copper foil.
Preferably, the thickness of the modified copper foil in the third step is 12.5 to 15 μm, more preferably 13 to 15 μm.
Preferably, the component formulation of LS-002 in step four is preferably 1.0M LiTFSI in DOL:DME =1:1 vol% with 1.0% LiNO 3 。
Preferably, the cathode-free lithium ion battery obtained in the fourth step is CR2016 type.
The method for assembling the cathode-free lithium ion battery is not particularly limited, and the CR2016 type button battery which is a regenerated battery is formed by adopting the technical scheme well known in the art.
Preferably, the regenerated battery, that is, the CR2016 type button battery, is assembled in an argon atmosphere in an atmosphere of H 2 O<0.1 ppm, O 2 <0.1 ppm in a glove box.
The invention firstly provides a preparation method of a carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm, which is characterized in that waste graphite is recycled, namely a series of pretreatment and mechanical shearing stripping are carried out, so as to obtain a thin-layer graphene nano sheet with two-dimensional structural characteristics, wherein the thin-layer graphene nano sheet and graphite phase carbon nitride (g-C) 3 N 4 ) And carrying out electrostatic self-assembly to obtain the composite catalyst with the two-dimensional lamination structure. Then the lithium supplementing reagent lithium oxalate (Li 2 C 2 O 4 LCO) with a composite catalyst (SGr/g-C 3 N 4 ) Mixing with a first binder, utilizing intrinsic defects of the waste graphene nano sheets and the stripped two-dimensional thin layer structure as a conductive carbon substrate to integrally improve the conductivity of the catalyst, and simultaneously, cooperating with g-C at defect sites in waste graphite 3 N 4 The catalyst further accelerates the local electron transfer of the lithium supplementing reagent, thereby improving the lithium ion release rate of the lithium supplementing reagent. Sequentially coarse grinding and fine grinding the mixed powder to obtain ground powder, mixing with a first organic solvent, sequentially performing first stirring and first defoaming stirring to obtain uniform slurry with certain viscosity, coating a functionalized lithium supplementing interface layer on a PP base film (diaphragm), and performing first vacuum drying to obtain a PP base lithium supplementing diaphragm (SGr/g-C for short) with rapid lithium supplementing rate 3 N 4 -LCO)。
The rapid lithium supplementing rate prepared based on the method provided by the inventionThe invention focuses on the problem of slow release rate of lithium in the existing lithium supplementing diaphragm, and introduces graphite-phase carbon nitride g-C without metal green catalyst 3 N 4 And the intrinsic structural characteristics of the waste graphite are utilized to develop a conversion route from the waste graphite to the high-added-value composite catalyst. By combining g-C 3 N 4 The catalytic PP-based high-efficiency lithium supplementing diaphragm is applied to battery manufacturing, and the catalyst accelerates Li in the first-circle lithium supplementing process + Kinetics of release and reduction of high voltage lithium supplementation reagent Li 2 C 2 O 4 The decomposition voltage of the lithium-supplementing diaphragm can be applied to a wider voltage window range, and the application universality of the lithium-supplementing diaphragm in various battery systems is realized. And can construct high-energy dense non-negative electrode lithium ion battery with good cycle stability. In addition, the g-C prepared by the method provided by the invention 3 N 4 The preparation process of the catalytic PP-based high-efficiency lithium supplementing diaphragm is simple, the formula of the customized lithium supplementing catalyst can be matched with the current battery manufacturing process according to a specific battery system and application scene, the catalytic PP-based high-efficiency lithium supplementing diaphragm is suitable for large-scale production and commercial application, and a feasible reference template is provided for the negative electrode recovery of the waste lithium ion battery.
The invention has the beneficial effects that:
the present invention contemplates exfoliated-lamellar graphite-phase carbon nitride g-C 3 N 4 High electronegativity N element in two-dimensional thin layer characteristics and structures for modification of copper foil to facilitate uniform Li + And the flux is uniformly deposited to obtain a modified copper foil, and then the two strategies of the carbon nitride-catalyzed PP-based high-efficiency lithium supplementing diaphragm and the copper foil modification (namely, the modified copper foil is prepared) are combined, so that the cathode-free lithium ion battery with excellent cycle stability and high energy density is constructed.
Aiming at the existing technical problem of the lithium supplementing diaphragm, namely the problem of slow release rate of lithium ions, the invention introduces the graphite phase carbon nitride g-C without a metal green catalyst 3 N 4 To accelerate the kinetics of lithium ion release. The residual lithium and defect-rich structural characteristics of the waste graphite are deeply excavated, and the method is respectively applied to high-efficiency lithium supplementing diaphragm and modified copper foil modificationAnd the lithium ion battery is beneficial to the rapid and sufficient release of active lithium of the lithium supplementing diaphragm and the uniform deposition of lithium, so that the waste graphite is transformed into a high-energy battery cell with higher added value. The stripping process combined with mechanical shearing is adopted, so that the structural characteristics of the material are greatly upgraded, and the use of each application end is met; the method provided by the invention has the advantages that the cathode-free lithium ion battery constructed by the high-efficiency lithium supplementing diaphragm and the modified copper foil shows excellent cycle stability and high energy density, solves the key technical problem of the lithium supplementing technology, realizes the high added value conversion of waste graphite, realizes the design and application of the cathode-free lithium ion battery with high energy density, and provides an innovative method which has important significance for the supply chain cycle of the battery, the urgent energy demand and the environmental protection.
The results of the examples show that SGr/g-C prepared in example 1 of the present invention 3 N 4 Electrolyte wetting angle of LCO diaphragm was reduced from 34 deg. to 13.29 deg., composite catalyst SGr/g-C prepared in example 1 3 N 4 Adding lithium oxalate Li 2 C 2 O 4 In SGr/g-C 3 N 4 The slope of the Tafel curve (overpotential, η) of the LCO diaphragm is 317 mV dec -1 The negative electrode-free lithium ion battery prepared in application example 1-1 exhibited excellent lithium replenishing kinetics, and still exhibited excellent cycle stability (75.13% capacity retention at 1C rate) after a cycle time exceeding 60 cycles.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 shows a two-dimensional laminated structure of a composite catalyst SGr/g-C prepared in example 1 of the present invention 3 N 4 A surface TEM image;
FIG. 2 shows a two-dimensional laminated structure of a composite catalyst SGr/g-C prepared in example 1 of the present invention 3 N 4 Surface AFM map;
FIG. 3 is a graph of SGr/g-C prepared in example 1 of the present invention 3 N 4 -a surface SEM image and a cross-sectional SEM image of an LCO separator, wherein a in fig. 3 is a planar SEM image and b in fig. 3 is a cross-sectional SEM image;
FIG. 4 shows the present inventionComparative example 2 and comparative example 1, wherein a in FIG. 4 is the PP film wetting angle in comparative example 2 and b in FIG. 4 is SGr/g-C prepared in example 1 3 N 4 -LC diaphragm wetting angle;
FIG. 5 is a Tafel curve comparison of comparative example 1 and example 1 of the present invention;
fig. 6 is a graph comparing the cycle stability of the lithium ion battery without negative electrode prepared in comparative example 2-1 and application example 1-1.
Detailed Description
The invention will be further described with reference to the drawings and examples. Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The above-mentioned features of the invention or the features mentioned in the specific examples can be combined in any desired manner, and these specific examples are only intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
The invention provides a preparation method of a carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm, which comprises the following steps: s1, discharging a waste lithium ion battery to 0.16V in a sodium chloride (NaCl) solution, sequentially carrying out disassembly, crushing and screening to obtain waste graphite powder, calcining the waste graphite powder at 600 ℃ to remove organic components such as a residual binder, electrolyte and the like in the waste graphite, and stripping the obtained waste graphite powder in a water/dispersant mixed solvent system through mechanical shearing force of a homogenizer to obtain a thin-layer graphene nano sheet;
s2 200 mg of S1 was processed to give thin graphene nanoplatelets and 100 mg graphite phase carbon nitride (g-C) 3 N 4 ) Electrostatic self-assembly by ultrasonic stripping in water/ethanol mixed solvent to obtain composite catalyst (SGr/g-C) 3 N 4 )；
S3 will 700 mg Li 2 C 2 O 4 Coarsely grinding 200 mg of the composite catalyst obtained in S2 and 100 mg polyvinylidene fluoride PVDF in a mortar, and finely grinding in a ball mill at 400-600 r/min for 18-h to obtain ground powder; two-dimensional composite catalyst, lithium oxalate and method for preparing the sameThe mass ratio of the first binder PVDF is 2:7:1, a step of;
s4, adding the ground powder obtained in the step S3 into a first organic solvent NMP of 1.2 mL, performing first stirring at 600 r/min for 12: 12h until the solid is dissolved, and then performing first defoaming stirring in a homogenizer for 30 min to obtain uniform slurry;
s5, carrying out cross spraying on the slurry obtained in the S4 on the surface of the PP base film through ultrasonic film spraying equipment to form a lithium supplementing interface layer with the thickness of 5 mu m, wherein the flow rate of ultrasonic spraying is 0.5mL/min, and the speed of ultrasonic spraying is 15000mm/min; after the ultrasonic spraying is completed, the ultrasonic-sprayed product is put into a vacuum drying oven to be subjected to first vacuum drying at 60 ℃ for 12h, and g-C with the thickness of 15 mu m is obtained 3 N 4 Catalytic PP-based high-efficiency lithium supplementing diaphragm (SGr/g-C for short) 3 N 4 -LCO)。
Application example 1-1
The g-C obtained in example 1 3 N 4 The catalytic PP-based high-efficiency lithium supplementing diaphragm is applied to a non-negative electrode lithium ion battery, and the preparation method comprises the following steps:
step one, commercial block graphite phase carbon nitride g-C 3 N 4 Carbon nitride g-C of bulk graphite phase in water/ethanol mixed solvent by mechanical shearing force through homogenizer 3 N 4 Stripping to obtain lamellar graphite phase carbon nitride g-C 3 N 4 A nanosheet;
step two, the step 540 and mg is carried out to obtain the thin layer graphite phase carbon nitride g-C 3 N 4 The nano-sheets and 60 mg CMC are dispersed into a second organic solvent NMP of 0.8 mL, and mixed slurry which is uniform and has certain viscosity is obtained under the second defoaming stirring in the homogenate; lamellar graphite phase carbon nitride g-C 3 N 4 And a second binder CMC in a mass ratio of 9:1;
step three, carrying out cross spraying on the mixed slurry obtained in the step two on a copper foil in an ultrasonic spraying mode to form an ultrathin decorative layer with the thickness of 5 mu m, wherein the ultrasonic spraying flow is 0.5mL/min, and the ultrasonic spraying speed is high: 16000 After the ultrasonic spraying is finished, carrying out second vacuum drying on the ultrasonic sprayed product for 12 hours at the temperature of 80 ℃ under the vacuum condition to obtain a modified copper foil with the thickness of 15 mu m;
step four, lithium iron phosphate, g-C prepared in example 1 3 N 4 Catalytic PP-based high performance lithium-supplementing separator (SGr/g-C 3 N 4 LCO), and respectively taking the modified copper foil obtained in the step three as a positive electrode, a diaphragm and a negative electrode, and adopting LS-002 as electrolyte to assemble the CR2016 type non-negative electrode lithium ion battery.
Example 2
Prepared according to the method of example 1, except for example 1: s3 with 450 mg Li 2 C 2 O 4 450 mg composite catalyst and 100 mg polyvinylidene fluoride (PVDF), the mass ratio of the two-dimensional composite catalyst, lithium oxalate and the first binder PVDF was 4.5:4.5:1.
application example 2-1
A negative electrode-free lithium ion battery was prepared in the same manner as in application example 1, except that: in step four, g-C prepared in example 2 was used 3 N 4 The catalyzed PP-based high-efficiency lithium supplementing diaphragm is used as a diaphragm.
Example 3
Prepared according to the method of example 1, except for example 1: s3 with 600 mg Li 2 C 2 O 4 300 and mg composite catalyst and 100 mg PVDF, wherein the mass ratio of the two-dimensional composite catalyst to the lithium oxalate to the first binder PVDF is 3:6:1.
application example 3-1
A negative electrode-free lithium ion battery was prepared in the same manner as in application example 1, except that: in step four, g-C prepared in example 3 was used 3 N 4 The catalyzed PP-based high-efficiency lithium supplementing diaphragm is used as a diaphragm.
Comparative example 1
750 mg of Li 2 C 2 O 4 And 250 mg PVDF sequentially passes through coarse grinding, fine grinding, first stirring, first defoaming stirring and ultrasonic spraying, an ultrathin lithium supplementing interface layer is coated on the PP base film, and a lithium supplementing diaphragm, namely a pure LCO diaphragm, is prepared through first vacuum drying; wherein the ginseng is coarsely ground, finely ground, first stirred, first defoamed stirred, ultrasonically sprayed and first vacuum driedThe numbers are the same as in example 1.
Comparative examples 1 to 1
A negative electrode-free lithium ion battery was prepared in the same manner as in application example 1-1, except that: the lithium-compensating separator prepared in comparative example 1 was used as a separator.
Comparative example 2
The PP separator (i.e., PP base film) and the copper foil were washed with absolute ethanol and dried in vacuo, except that no treatment was performed.
Comparative example 2-1
A negative electrode-free lithium ion battery was prepared in the same manner as in application example 1-1, except that: the PP separator of comparative example 2 was used as a separator, and the copper foil of comparative example 2 was used as a negative electrode.
Comparative example 3
Preparing a modified copper foil: 540 mg thin layer graphite phase carbon nitride g-C 3 N 4 And 60 mg CMC is dispersed into NMP to form mixed solution, uniform slurry with certain viscosity is obtained under the high-speed defoaming and stirring of a refiner, a layer of ultrathin (5 mu m) modification layer (cross spraying, spraying flow: 0.5mL/min and spraying speed: 16000 mm/min) is coated on the copper foil by ultrasonic spraying, and finally the modified copper foil is obtained after drying for 12 hours under the vacuum condition of 80 ℃; the PP separator and the modified copper foil were washed with absolute ethanol and dried in vacuo, except that no treatment was performed.
Characterization experiments
Transmission Electron Microscope (TEM) characterization:
the TEM image obtained by observing the surface of the two-dimensional composite catalyst prepared in example 1 of the present invention by a transmission electron microscope is shown in FIG. 1. As can be seen from FIG. 1, in example 1, the waste graphite powder and the bulk graphite phase carbon nitride g-C are treated by a homogenizer 3 N 4 Mechanical shearing stripping is carried out, and the obtained thin-layer graphene nano sheet and thin-layer graphite phase carbon nitride g-C 3 N 4 The lithium oxalate composite material has a good two-dimensional laminated structure, has a large surface area, is favorable for subsequent mixing with lithium oxalate, promotes local electron transfer, and realizes rapid and efficient release of more active Li + Is used for supplementing lithium.
Atomic Force Microscope (AFM) characterization:
the surface structure and the sheet thickness of the two-dimensional composite catalyst prepared in example 1 of the present invention were observed by an atomic force microscope to obtain an AFM image as shown in FIG. 2, and it is understood from FIG. 2 that in example 1, the waste graphite powder and the bulk graphite phase carbon nitride g-C were subjected to a homogenizer 3 N 4 The mechanical shearing stripping is carried out, the obtained composite thin layer catalyst presents a good two-dimensional laminated structure, the thickness of the thin layer graphene nano sheet is about 5.6 nm, and the thin layer graphite phase carbon nitride g-C 3 N 4 About 7.8 and nm, the stacked structure is favorable for the two materials to exert respective structural characteristics to the maximum extent, the thin-layer graphene nano sheet improves the low conductivity of the carbon nitride, and the electrocatalytic property of the materials is integrally and synergistically improved, so that the lithium supplementing diaphragm release activity Li is improved + Is a dynamic of (a).
Scanning Electron Microscope (SEM) characterization:
SGr/g-C prepared in example 1 was observed by a scanning electron microscope 3 N 4 As shown in FIG. 3, wherein a in FIG. 3 is a plan SEM image and b in FIG. 3 is a cross-sectional SEM image, it is understood from FIG. 3 that example 1, after forming an efficient lithium-compensating interface layer by ultrasonic spray coating, the slurry was uniformly coated on the separator without cracks, and the lithium-compensating interface layer was tightly adhered to the PP separator, the thickness of the obtained lithium-compensating coating layer was about 10 μm, and g-C (thickness 20 μm) was obtained in the final example 1 3 N 4 The preparation of the catalytic PP-based high-efficiency lithium supplementing diaphragm has the advantages that the requirements of high energy density cells can be met due to rapid lithium release kinetics and high lithium supplementing surface capacity.
Diaphragm-electrolytic contact angle characterization:
the PP film in comparative example 2 was examined with SGr/g-C prepared in example 1 by the optical contact angle measurement method 3 N 4 The contact angle of the electrolyte wetting membrane of the LCO membrane is shown in FIG. 4, and it can be seen from FIG. 4 that the homogeneously distributed lithium-compensating interface layer enables SGr/g-C prepared in example 1, compared to the PP membrane in comparative example 2 3 N 4 The wettability of the electrolyte of the LCO separator is greatly improved, the contact angle is reduced from 34 degrees to 13.29 degrees,SGr/g-C 3 N 4 the LCO lithium supplementing diaphragm has the function of efficiently transferring lithium ions, so that the service performance of the LCO lithium supplementing diaphragm is improved.
Characterization of electrochemical properties:
the pure LCO diaphragm prepared in comparative example 1 and SGr/g-C prepared in example 1 were detected by Tafel polarization curve test method 3 N 4 Tafel polarization curve of LCO diaphragm is shown in FIG. 5, and it can be seen from FIG. 5 that high efficiency SGr/g-C prepared in example 1 3 N 4 Tafel slope (overpotential, η) of LCO diaphragm is 317 mV dec -1 Lower than the pure LCO membrane of comparative example 1 (η=634 mV dec -1 ) Description is made of the incorporation of a composite catalyst (SGr/g-C) 3 N 4 ) Li with acceleration + Release kinetics such that SGr/g-C in example 1 3 N 4 Higher electrocatalytic activity at the LCO membrane interface.
To evaluate the lithium supplementing performance of the PP separator in comparative example 2 and the SGr/LFO separator prepared in example 1, a thin layer of graphite-phase carbon nitride g-C 3 N 4 Compared with a cycle stability graph of the modified copper foil with respect to the action of uniform lithium deposition stripping behavior, the cathode-free lithium ion battery (abbreviated as lithium iron phosphate (PP) diaphragm) prepared in comparative example 2-1 and the cathode-free lithium ion battery (abbreviated as lithium iron phosphate (SGr)/g-C) prepared in application example 1-1 are tested at a magnification of 1C 3 N 4 LCO separator modified copper foil) as shown in fig. 6, rapid capacity decay of the non-negative lithium ion battery of comparative example 2-1 during cycling and eventually battery short-circuiting can be clearly observed from fig. 6; in contrast, the negative electrode-free lithium ion battery prepared in application example 1-1 exhibited a higher specific capacity and excellent cycle stability (75.13% capacity retention at 1C rate) after more than 60 cycles, indicating that SGr/g-C was obtained as a result of the preparation of example 1 3 N 4 The catalytic action of the thin-layer two-dimensional composite catalyst in the LCO diaphragm on the lithium supplementing reagent, so that Li in the lithium supplementing diaphragm + Can effectively supplement the unavoidable lithium loss of the positive electrode in the circulating process, and the lamellar graphite phase carbon nitride g-C 3 N 4 The N element in (2) can be pre-summedThe solvated lithium ions form Li-N bonds, so that the lithium deposition behavior is effectively and uniformly achieved, side reactions of lithium dendrite formation are suppressed, and long-acting circulation of the high-energy-density non-negative electrode battery is realized.
As described above, SGr/g-C prepared in example 1 of the present invention 3 N 4 The electrolyte wettability of the LCO diaphragm is greatly improved, the contact angle is reduced from 34 degrees to 13.29 degrees, and the composite catalyst SGr/g-C 3 N 4 Is added to obviously improve lithium oxalate Li 2 C 2 O 4 Kinetics of lithium Release of lithium-supplementing reagent SGr/g-C 3 N 4 The slope of the Tafel curve (overpotential, η) of the LCO diaphragm is 317 mV dec -1 The negative electrode-free lithium ion battery prepared in application example 1-1 still exhibits a higher energy density and excellent cycle stability (75.13% capacity retention at 1C rate) after a cycle time exceeding 60 cycles.
The method provided by the invention prepares the carbon nitride catalyzed PP-based high-efficiency lithium supplementing diaphragm (namely SGr/g-C) 3 N 4 LCO) by introducing a metal-free green catalyst graphite phase carbon nitride (g-C) 3 N 4 ) And recovering and stripping the obtained thin graphene nano sheet (SGr) to obtain a composite catalyst with a two-dimensional laminated structure through electrostatic action, and then mixing the obtained composite catalyst with a commercial lithium supplementing reagent lithium oxalate (Li 2 C 2 O 4 LCO) and coating a layer of functionalized high-efficiency lithium supplementing interface layer on the PP-based (separation) film by ultrasonic spraying to prepare SGr/g-C 3 N 4 LCO; by adding the functional high-efficiency lithium-supplementing diaphragm SGr/g-C 3 N 4 LCO is applied to battery manufacturing, and a lithium supplementing diaphragm releases a proper amount of active Li in the first-circle charge and discharge process + Matching the graphite phase of the carbon nitride (g-C) 3 N 4 ) The modified copper foil can be used for constructing a non-negative electrode lithium ion battery with higher energy density, and the non-negative electrode lithium ion battery has excellent cycle stability and rate capability.
In addition, the functional high-efficiency lithium supplementing diaphragm SGr/g-C prepared by the method provided by the invention 3 N 4 The LCO has simple preparation process and is similar to the current battery manufacturingThe process is compatible, is suitable for industrialized large-scale application, solves the key problem existing in the current lithium supplementing technology, simultaneously deeply digs the high added value of the waste graphite, and meets the urgent requirement on the high-energy-density battery cell, thereby providing a brand new feasible solution for the sustainable supply chain of the lithium ion battery.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (10)
1. The preparation method of the carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm is characterized by comprising the following steps of:
s1: pretreating waste graphite and mechanically shearing and stripping to obtain a thin-layer graphene nano sheet;
s2: c, the thin-layer graphene nano sheet obtained in the step S1 and graphite phase carbon nitride g-C 3 N 4 Performing electrostatic self-assembly to obtain a composite catalyst with a two-dimensional lamination structure;
s3: composite catalyst obtained by S2 and lithium oxalate Li 2 C 2 O 4 Mixing with a first binder, and sequentially carrying out coarse grinding and fine grinding to obtain ground powder;
s4: mixing the ground powder obtained in the step S3 with a first organic solvent, and then sequentially carrying out first stirring and first defoaming stirring to obtain slurry;
s5: coating the slurry obtained in the step S4 on the surface of a PP base film to form a lithium supplementing interface layer; after the coating is completed, the coated product is subjected to first vacuum drying to obtain g-C 3 N 4 Catalytic PP-based high-efficiency lithium supplementing diaphragm.
2. The method for preparing the carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm, which is characterized in that: in S1, waste graphite is obtained by recycling the negative electrode of a waste lithium ion battery, and the method comprises the following steps: discharging the waste lithium ion battery in sodium chloride solution, and then sequentially carrying out disassembly, crushing, screening and calcination to obtain waste graphite powder; and the mechanical stripping is to strip the obtained waste graphite powder in a water/dispersant mixed solvent system through mechanical shearing force of a homogenizer to obtain the thin-layer graphene nano sheet.
3. The method for preparing the carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm, which is characterized in that: in S2, electrostatic self-assembly is carried out on the thin-layer graphene nano sheet and graphite phase carbon nitride g-C in a water/ethanol mixed solvent through ultrasonic stripping 3 N 4 Electrostatic self-assembly is carried out to obtain the composite catalyst SGr/g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the Thin graphene nanoplatelets and graphite phase carbon nitride g-C 3 N 4 The mass ratio of (1-2): 1.
4. the method for preparing the carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm, which is characterized in that: s3 composite catalyst, lithium oxalate Li 2 C 2 O 4 And the mass ratio of the first binder is 2-5: 3-7: 1, a step of; the first binder is at least one of polyvinylidene fluoride, polyvinyl acetate and polyvinylidene chloride-hexafluoropropylene copolymer.
5. The method for preparing the carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm, which is characterized in that: and S4, the rotating speed of the first stirring is 500-1000 r/min, and the time of the first stirring is 11-14 h.
6. The method for preparing the carbon nitride catalysis PP-based high-efficiency lithium supplementing diaphragm, which is characterized in that: the coating mode in the step S5 is ultrasonic spraying, the flow rate of the ultrasonic spraying is 0.2-1.0 mL/min, and the speed of the ultrasonic spraying is 10000-15000 mm/min; the thickness of the lithium-supplementing interface layer is 5-12 μm.
7. A g-C prepared by a method for preparing a carbon nitride catalyzed PP-based high performance lithium supplementing diaphragm according to any one of claims 1-6 3 N 4 The application of the catalytic PP-based high-efficiency lithium supplementing diaphragm is characterized in that: the method is applied to the non-negative electrode lithium ion battery.
8. The g-C of claim 7 3 N 4 The application of the catalytic PP-based high-efficiency lithium supplementing diaphragm is characterized in that: the preparation method of the cathode-free lithium ion battery comprises the following steps:
step one, the bulk graphite phase carbon nitride g-C 3 N 4 Mechanical shearing stripping is carried out to obtain the thin-layer graphite phase carbon nitride g-C 3 N 4 A nanosheet;
step two, the thin layer graphite phase carbon nitride g-C obtained in the step one 3 N 4 Mixing the nanosheets, the second binder and the second organic solvent, and then performing second defoaming stirring to obtain mixed slurry;
thirdly, ultrasonically spraying the mixed slurry obtained in the second step on the surface of the copper foil to form a lithium regulating layer; after the ultrasonic spraying is finished, carrying out second vacuum drying on the ultrasonic-sprayed copper foil to obtain a modified copper foil;
step four, lithium iron phosphate and g-C 3 N 4 The catalyzed PP-based high-efficiency lithium supplementing diaphragm and the modified copper foil obtained in the step three are respectively used as a positive electrode, a diaphragm and a negative electrode, LS-002 is used as electrolyte, and the cathode-free lithium ion battery is constructed.
9. The g-C of claim 8 3 N 4 The application of the catalytic PP-based high-efficiency lithium supplementing diaphragm is characterized in that: in the second step, the lamellar graphite phase carbon nitride g-C 3 N 4 The mass ratio of the nano sheet to the second binder is 7-12:1.
10. The g-C of claim 8 3 N 4 The application of the catalytic PP-based high-efficiency lithium supplementing diaphragm is characterized in that:and in the third step, the thickness of the lithium regulating layer is 3-5 mu m.
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