CN115832314B - Composite graphite alkyne modified layered oxide material, preparation method thereof, positive plate and sodium ion battery - Google Patents
Composite graphite alkyne modified layered oxide material, preparation method thereof, positive plate and sodium ion battery Download PDFInfo
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- CN115832314B CN115832314B CN202310150560.4A CN202310150560A CN115832314B CN 115832314 B CN115832314 B CN 115832314B CN 202310150560 A CN202310150560 A CN 202310150560A CN 115832314 B CN115832314 B CN 115832314B
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Abstract
The invention discloses a composite graphite alkyne modified layered oxide material, which has a molecular formula of M x ‑GDY@NaNi a Fe b Mn c O 2 Wherein: m is at least one of H and alkali metal elements, and x is more than or equal to 0.01 and less than or equal to 1; 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1. The invention also discloses a preparation method of the composite graphite alkyne modified layered oxide material, and a positive plate and a sodium ion battery prepared from the composite graphite alkyne modified layered oxide material. The composite graphite alkyne modified layered oxide material can improve the capacity and the first coulomb efficiency of a sodium ion battery and prolong the service life of the battery.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a composite graphite alkyne modified layered oxide material and a preparation method thereof, an anode plate and a sodium ion battery.
Background
Among various positive electrode materials of sodium ion batteries, O3-phase layered oxides have received attention because they can provide sufficient sodium in a full battery, have high electrochemical activity, have high theoretical specific capacities, and are easy to synthesize. However, the problems of low energy density and low full battery life limit the practical application of the O3 phase layered oxide.
Therefore, how to increase the energy density of the O3 phase layered oxide cathode material and increase the lifetime of the sodium ion full cell becomes one of the key problems in the related art of sodium ion cells.
Disclosure of Invention
The invention aims to solve the technical problem of providing a composite graphite alkyne modified layered oxide material which is used as a positive electrode material of a sodium ion battery, can improve the capacity and the first coulomb efficiency of the sodium ion battery and prolongs the service life of the whole battery.
In order to solve the technical problems, the invention provides the following technical scheme:
the first aspect of the invention provides a composite graphite alkyne-modified layered oxide material, which has a molecular formula of M x -GDY@NaNi a Fe b Mn c O 2 Wherein: m is at least one of H and alkali metal elements, and x is more than or equal to 0.01 and less than or equal to 1; 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1.
Further, the D50 particle size of the composite graphite alkyne modified layered oxide material is 0.01-100.5 mu m;
and/or the specific surface area of the composite graphite alkyne modified layered oxide material is 0.01-16.9 m 2 /g。
The second aspect of the invention provides a preparation method of a composite graphite alkyne-modified layered oxide material, which comprises the following steps:
s1, under vacuum or inert atmosphere, the hexahalobenzene and carbide M are reacted 2 C 2 Mixing with absolute ethyl alcohol, ball milling, washing to remove unreacted carbide M 2 C 2 The method comprises the steps of carrying out a first treatment on the surface of the Then, the ball-milling product is dried and ground at the temperature of 40-120 ℃, and then the unreacted hexahalobenzene is removed by washing; then, the ground product is dried at the temperature of 40 to 120 ℃ to obtain M x -GDY powder;
s2. M x GDY powder, naNi a Fe b Mn c O 2 Mixing the powder, and performing wet ball milling; drying to obtain a composite graphite alkyne modified layered oxide material;
wherein in step S1, the carbide M 2 C 2 At least one of acetylene, lithium carbide, sodium carbide and potassium carbide; x is more than or equal to 0.01 and less than or equal to 1;
in step S2, 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1.
Further, in step S1, carbide M 2 C 2 The molar ratio of the benzene to the hexahalobenzene is 1-18:1-6;
and/or removing unreacted carbide M by water washing 2 C 2 ；
And/or the rotation speed of the ball milling is 200-3000 rpm, and the ball milling time is 4-18 h.
Further, in step S2, the solvent of the wet ball milling is ethanol;
and/or the rotating speed of the wet ball milling is 100-3000 rpm, and the time of the wet ball milling is 0.5-48 h;
and/or the temperature of the drying is 40-120 ℃.
Further, in step S2, the NaNi a Fe b Mn c O 2 The preparation method of the powder comprises the following steps:
a. mixing sodium salt with metal salt, ball milling and stirring uniformly; the metal salt comprises at least one of nickel salt, iron salt and manganese salt;
b. sintering the mixture obtained in the step a at 800-1200 ℃ to obtain the NaNi a Fe b Mn c O 2 A powder;
wherein in the step a, the sodium salt comprises at least one of sodium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfide, sodium sulfite, sodium bisulphite, sodium nitrite, sodium chlorate, sodium ferrate, sodium fluoride, sodium bromide and sodium iodide;
and/or the nickel salt comprises at least one of nickel oxide, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide and nickel carbonyl;
and/or the ferric salt comprises at least one of ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate and ferrous oxalate;
and/or the manganese salt comprises at least one of manganese oxide, potassium permanganate and potassium manganate;
and/or the molar ratio of the sodium salt to the metal salt is 0.05-1.25:0.01-1.
Further, in step S2, the NaNi a Fe b Mn c O 2 Preparation of the powderThe method comprises the following steps:
c. mixing sodium salt with precursor salt, ball milling and stirring uniformly;
d. sintering the mixture obtained in the step c at 800-1200 ℃ to obtain the NaNi a Fe b Mn c O 2 A powder;
wherein the sodium salt comprises at least one of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate;
and/or the precursor salt comprises at least one of nickel oxide, manganese oxide, iron oxide, nickel iron oxide, manganese iron oxide, nickel manganese oxide, nickel iron manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron hydroxide, manganese iron hydroxide, nickel manganese hydroxide and nickel iron manganese hydroxide;
and/or the molar ratio of the sodium salt to the precursor salt is 0.01-1.25:0.01-1.
Further, in steps a and c:
the rotation speed of the ball milling is 100-1000 rpm, and the time of the ball milling is 0.2-3 h;
in steps b and d:
the temperature rising rate of the sintering is 0.01-10 ℃/min, and the sintering time is 0.5-48 h.
The third aspect of the invention provides a positive plate comprising the composite graphite alkyne-modified layered oxide material or the composite graphite alkyne-modified layered oxide material prepared by the method.
According to a fourth aspect of the invention, there is provided a sodium ion battery comprising the positive electrode sheet described above.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the graphite alkyne material is introduced to carry out composite modification on the layered oxide, so that the structural stability of the layered oxide is improved, and the service life of the full battery is greatly optimized.
2. In the composite graphite alkyne modified layered oxide material, the existence of alkali metal in the composite graphite alkyne generates a pre-alkali metal effect, so that the energy density of the material can be improved, and the capacity and the first coulomb efficiency of a battery are improved.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of graphite diyne;
FIG. 2 is a diagram of example 1 material Li 0.18 -Scanning Electron Microscope (SEM) and Mapping images of GDY;
FIG. 3 is a material Li of example 1 0.18 -GDY energy spectrum (EDS);
FIGS. 4a and 4b show Li in example 1 0.18 -SEM images of gdy@nnfm material; FIG. 4c is an SEM image of a cut surface of the material; FIG. 4d is a simplified drawing of the section mapping; FIGS. 4e and 4f are Transmission Electron Microscope (TEM) diagrams of the material;
FIG. 5 is Li in example 1 0.18 -Raman (Raman) spectra of GDY material;
FIG. 6 is Li in example 1 0.18 -an X-ray photoelectron spectroscopy (XPS) spectrum of a gdy@nnfm material;
FIG. 7 is Li in example 1 0.18 -X-ray diffraction pattern (XRD) of gdy@nnfm material.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The O3 phase layered oxide has the problems of low energy density, poor service life of the whole battery and the like, and limits the practical application thereof. At present, the prior art adopts means such as element doping and coating to modify the O3 phase layered oxide, but the means can only slightly improve the energy density, but can not solve the problem of poor service life of the whole battery, and particularly forms a new system with hard carbon materials in practical application.
In order to solve the problems of the layered oxide, the invention provides a modification method of the layered oxide, wherein the layered oxide is coated and modified by introducing a composite graphite alkyne material, so that the stability of the layered oxide is improved, and the service life of a full battery is prolonged; meanwhile, the layered oxide has the effect of pre-alkali metallization by introducing the composite graphite alkyne, so that the energy density and the first coulombic efficiency of the battery are improved.
Specifically, the molecular formula of the composite graphite alkyne-modified layered oxide material provided by the invention is M x -GDY@NaNi a Fe b Mn c O 2 Wherein: m is at least one of H and alkali metal elements, and x is more than or equal to 0.01 and less than or equal to 1; 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1.
In the invention, naNi a Fe b Mn c O 2 (NNFM) is a layered oxide comprising O3 phase layered oxide, P2 phase layered oxide, e.g. NaMnO 2 、NaFeO 2 、NaNiO 2 、NaFe 1/2 Mn 1/2 O 2 Etc.
Graphite alkyne (GDY) is composed of sp and sp 2 The novel all-carbon material consisting of hybridized carbon atoms is equivalent to all-carbon polymers with two-dimensional planar network structures formed by conjugated connection of benzene rings by alkyne bonds. Therefore, the graphite alkyne has a large number of chemical bonds of carbon, a large conjugated system and a wide-surface spacing, and has good chemical stability. Of the graphite alkynes, graphite diyne (. Gamma. -GDY) is the most stable and has a low energy of formation (DeltaHf= 919.2 kJ/mol), and is therefore the easiest to synthesize. The structural formula of graphite diacetylene is shown in figure 1.
Because of the cross coupling reaction on the alkynyl site of the graphite alkyne, a sub-angstrom-level ion channel can be formed, and another high-speed channel is provided for ion migration, so that the ion migration efficiency is improved. Therefore, the graphite alkyne is used for coating and modifying the layered oxide, so that the ionic conductivity of the layered oxide can be improved. In addition, the double fixation of covalent bonds and pi conjugated structures in alkyne and aryl structures in the graphite alkyne ensures the interface stability under GDY high-quality load, ensures the stability of the interface and structure of the layered oxide material, and is beneficial to prolonging the cycle life of the battery.
In the present invention, M x GDY is H or an alkali metal (Li, na, K) complex graphite alkyne, the structure of which is presumed to be H or an alkali metal element bonded to an alkyne group at the periphery of GDY molecules. Wherein when M is an alkali metal, the process corresponds to the process of performing 'pre-alkali metallization' on GDY, so that the energy density of the layered oxide material can be improved, and the capacity and the first coulombic efficiency of the battery can be improved.
In the present invention, the D50 particle diameter of the composite graphite alkyne-modified layered oxide material is preferably in the range of 0.01 to 100.5. Mu.m, for example, 0.1 to 1. Mu.m, 1 to 5. Mu.m, 5 to 10. Mu.m, 10 to 20. Mu.m, 20 to 30. Mu.m, 30 to 50. Mu.m, 50 to 60. Mu.m, 60 to 80. Mu.m, 80 to 100.5. Mu.m, etc.
In the invention, the specific surface area of the composite graphite alkyne modified layered oxide material is preferably in the range of 0.01 to 16.9 and 16.9m 2 For example, the ratio of the total amount of the components per gram is 0.01 to 0.1. 0.1 m 2 /g、0.1～1 m 2 /g、1～2 m 2 /g、2～4 m 2 /g、4～5 m 2 /g、5～8 m 2 /g、8～10 m 2 /g、10～12 m 2 /g、12～15 m 2 /g、15～16.9 m 2 /g, etc.
The invention also discloses a preparation method of the composite graphite alkyne modified layered oxide material, which comprises the following steps:
s1, under vacuum or inert atmosphere, the hexahalobenzene and carbide M are reacted 2 C 2 Mixing with absolute ethyl alcohol, ball milling, washing to remove unreacted carbide M 2 C 2 The method comprises the steps of carrying out a first treatment on the surface of the Then, the ball-milling product is dried and ground at the temperature of 40-120 ℃, and then the unreacted hexahalobenzene is removed by washing; then, the ground product is dried at the temperature of 40 to 120 ℃ to obtain M x -GDY powder;
s2. M x GDY powder, naNi a Fe b Mn c O 2 Mixing the powder, and performing wet ball milling; and drying to obtain the composite graphite alkyne modified layered oxide material.
In the step S1, the chemical formula of the hexahalobenzene is C 6 X 6 Wherein X is halogen, such as F, cl, br, I, etc. Carbide M 2 C 2 Is acetylene, lithium carbide, sodium carbide and carbonAt least one of potassium salts. Carbide M 2 C 2 The molar ratio to the hexahalobenzene is preferably 1 to 18:1 to 6, and may be, for example, 18:1, 15:1, 10:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, 1:6, etc. The ball milling can be carried out in a ball milling tank or other containers, and a certain amount of ball milling medium, such as absolute ethyl alcohol, is added during ball milling, and the adding amount is suitable for the ball milling material to be used. The ball milling process is carried out under vacuum or inert atmosphere, so that the ball milling process needs to be carried out in a sealed ball milling tank, and vacuum pumping and/or inert gas such as nitrogen, argon and the like are/is carried out. In the ball milling process, the rotation speed of the ball milling can be selected to be 200-3000 rpm, such as 200 rpm, 500 rpm, 1000rpm, 1500 rpm, 2000 rpm, 2500 rpm, 3000rpm and the like; the ball milling time can be set to be 4-18 h, such as 4h, 6h, 8h, 10h, 12h, 15h, 18h and the like. In the ball milling process, the reaction is carbide M 2 C 2 The alkynyl group in (a) replaces halogen in the hexahalobenzene. After ball milling, unreacted carbide M can be removed by washing 2 C 2 。
The washed ball-milled product is first dried at 40-120 deg.c, e.g. 40 deg.c, 50 deg.c, 60 deg.c, 70 deg.c, 80 deg.c, 90 deg.c, 100 deg.c, 110 deg.c, 120 deg.c, etc. And grinding the dried ball-milling product to generate chemical reaction. Then, unreacted hexahalobenzene is removed by washing with an organic solvent, which may be a hot benzene solvent.
The washed ground product is then dried at a temperature of 40 to 120 ℃, for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ and the like.
Through the steps, the product is graphite alkyne M x GDY. Wherein, when carbide M 2 C 2 In the case of acetylene, the final product is graphite alkyne; when carbide M 2 C 2 In the case of lithium carbide, sodium carbide and potassium carbide, the final product is graphite alkyne bonded with alkali metal.
In step S2 of the invention, M x GDY powder, naNi a Fe b Mn c O 2 Mixing the powder by wet ball milling, and using ball milling mediumEthanol. The rotation speed of the wet ball milling is preferably 100 to 3000rpm, for example, 100rpm, 200 rpm, 500 rpm, 1000rpm, 1500 rpm, 2000 rpm, 2500 rpm, 3000rpm and the like can be used; the time of wet ball milling is preferably 0.5 to 48 hours, and may be, for example, 0.5 hours, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 18 hours, 24 hours, 30 hours, 40 hours, 48 hours, etc. After ball milling, the product is dried at a temperature of preferably 40 to 120 ℃, for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, etc.
In this step, M x GDY powder, naNi a Fe b Mn c O 2 After the powder is ball-milled and mixed, M x Coating of powder GDY on NaNi a Fe b Mn c O 2 To obtain the composite graphite alkyne modified layered oxide material.
In the invention, naNi a Fe b Mn c O 2 The powder may be prepared by two methods, one based on metal salt mixing and the other based on precursor salt mixing.
The method based on metal salt mixing comprises the following steps:
a. mixing sodium salt with metal salt, ball milling and stirring uniformly; the metal salt comprises at least one of nickel salt, iron salt and manganese salt;
b. sintering the mixture obtained in the step a at 800-1200 ℃ to obtain the NaNi a Fe b Mn c O 2 And (3) powder.
In the step a, the sodium salt includes at least one of sodium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfide, sodium sulfite, sodium bisulphite, sodium nitrite, sodium chlorate, sodium ferrate, sodium fluoride, sodium bromide and sodium iodide. Nickel salts include, but are not limited to, at least one of nickel oxide, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel carbonyl; iron salts include, but are not limited to, at least one of ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate, and ferrous oxalate; manganese salts include, but are not limited to, at least one of manganese oxide, potassium permanganate, potassium manganate.
In the step a, the sodium salt and the metal salt are prepared according to NaNi a Fe b Mn c O 2 The stoichiometric ratio in (0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1) is dosed. In some embodiments, the molar ratio of sodium salt to metal salt is 0.05-1.25:0.01-1. For example, in the preparation of the compound NaFeO 2 When sodium sulfate is used as sodium salt and ferric chloride is used as metal salt, the mixing mole ratio of the sodium salt to the metal salt is 1:2.
In the above step a, the rotation speed of the ball mill is preferably 100 to 1000rpm, and for example, 100rpm, 200 rpm, 400 rpm, 500 rpm, 600 rpm, 1000rpm, etc. may be used; the ball milling time is preferably 0.2 to 3h, and may be, for example, 0.2 hours, 0.5 hours, 1 hour, 2 hours, 3 hours, or the like.
In the step b, the temperature rising rate of the sintering is preferably 0.01 to 10 ℃ per minute, and for example, may be 0.01 ℃ per minute, 0.1 ℃ per minute, 0.5 ℃ per minute, 1 ℃ per minute, 2 ℃ per minute, 5 ℃ per minute, 10 ℃ per minute, etc.; the sintering time is preferably 0.5 to 48 and h, and may be, for example, 0.5h, 1h, 2h, 5h, 10h, 20h, 30h, 40h, 48h, etc.
The method based on precursor salt mixing comprises the following steps:
c. mixing sodium salt with precursor salt, ball milling and stirring uniformly;
d. sintering the mixture obtained in the step c at 800-1200 ℃ to obtain NaNi a Fe b Mn c O 2 And (3) powder.
In the step c, the sodium salt includes at least one of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate. The precursor salt includes, but is not limited to, at least one of nickel oxide, manganese oxide, iron oxide, nickel iron oxide, manganese iron oxide, nickel manganese oxide, nickel iron manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron hydroxide, manganese nickel hydroxide, and nickel iron manganese hydroxide.
In the step c, the sodium salt and the precursor salt are prepared according to NaNi a Fe b Mn c O 2 The stoichiometric ratio in (0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1) is dosed. In some embodiments, the molar ratio of sodium salt to precursor salt is 0.01-1.25:0.01-1. For example, in the preparation of the compound NaFe 1/2 Mn 1/2 O 2 When the sodium sulfate is used as sodium salt and the ferromanganese oxide is used as precursor salt, the mixing mole ratio of the sodium salt to the precursor salt is 1:1.
In the above step c, the rotation speed of the ball mill is preferably 100 to 1000rpm, and for example, 100rpm, 200 rpm, 400 rpm, 500 rpm, 600 rpm, 1000rpm, etc. may be used; the ball milling time is preferably 0.2 to 3h, and may be, for example, 0.2 hours, 0.5 hours, 1 hour, 2 hours, 3 hours, or the like.
In the step d, the temperature rising rate of the sintering is preferably 0.01 to 10 ℃ per minute, and for example, may be 0.01 ℃ per minute, 0.1 ℃ per minute, 0.5 ℃ per minute, 1 ℃ per minute, 2 ℃ per minute, 5 ℃ per minute, 10 ℃ per minute, etc.; the sintering time is preferably 0.5 to 48 and h, and may be, for example, 0.5h, 1h, 2h, 5h, 10h, 20h, 30h, 40h, 48h, etc.
On the basis of the composite graphite alkyne modified layered oxide material, the invention also provides a sodium ion battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the diaphragm is arranged to isolate the positive plate from the negative plate.
In the sodium ion battery, the positive plate can be prepared by adopting a common plate preparation process in the field. The preparation method is as follows: and mixing the composite graphite alkyne modified layered oxide material, the conductive agent and the binder to prepare slurry, coating the slurry on at least one side surface of the positive electrode current collector, and drying and tabletting to obtain the positive electrode plate.
The kind and content of the above-mentioned conductive agent are not particularly limited, and may be selected according to actual demands. In some embodiments, the conductive agent includes at least one of conductive carbon black, carbon nanotubes, acetylene black, graphene, ketjen black, carbon nanofibers, and the like. It will be appreciated that other conductive agents capable of performing the functions of the present application may be selected as desired without limitation without departing from the spirit of the present application.
The kind and content of the binder are not particularly limited and may be selected according to actual requirements. In some embodiments, the binder includes at least one of polyacrylonitrile, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethyl cellulose, polymethacrylate, polyacrylic acid, sodium polyacrylate, polyacrylamide, polyamide, polyimide, polyacrylate, styrene butadiene rubber, sodium alginate, chitosan, polyethylene glycol, guar gum, and the like.
The type of the positive electrode current collector is not particularly limited, and may be selected according to practical requirements, for example, the positive electrode current collector may be an aluminum foil, a nickel foil or a polymer conductive film, and preferably the positive electrode current collector is an aluminum foil.
In the sodium ion battery, the type of separator is not particularly limited, and any separator material used in conventional batteries, such as polyethylene, polypropylene, polyvinylidene fluoride, nonwoven fabric, multilayer composite films thereof, and modified separators such as ceramic modification and PVDF modification of the separator may be used.
In the sodium ion battery, the electrolyte can be one or more of organic liquid electrolyte, organic solid electrolyte, solid ceramic electrolyte and gel electrolyte. Preferably, the electrolyte is an organic liquid electrolyte obtained by dissolving sodium salt in a nonaqueous organic solvent; wherein the sodium salt may comprise sodium difluorophosphate (NaPO) 2 F 2 ) Sodium hexafluorophosphate (NaPF) 6 ) One or more of sodium bis (fluorosulfonyl) imide (NaFSI), sodium bis (trifluoromethanesulfonyl) imide (naftsi), and sodium difluoro (NaDFOB) oxalato borate (NaDFOB). The nonaqueous organic solvent may include one or more of cyclic carbonate, chain carbonate, and carboxylate. Wherein the cyclic carbonate can be selected from one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), butylene carbonate and gamma-butyrolactone; the chain carbonate may be selected from one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl Propyl Carbonate (MPC), methyl Acetate (MA), ethyl Acetate (EA), and Ethyl Propionate (EP).
In some embodiments, a certain amount of additives may also be added to the organic liquid electrolyte. The additive may include one or more of Vinylene Carbonate (VC), vinyl carbonate (VEC), vinyl sulfate (DTD), ethylene Sulfite (ES), methylene Methane Disulfonate (MMDS), 1, 3-Propane Sultone (PS), propylene sultone (PES), propylene sulfate (TMS), trimethylsilyl phosphate (TMSP), trimethylsilyl borate (TMSB), fluoroethylene carbonate (FEC).
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used, unless otherwise specified, are commercially available.
1. SEM and EDS test method
Grinding the materials into powder, taking a small amount of powder, placing the powder on a silicon wafer substrate stained with a conductive carbon tape, placing the silicon wafer substrate on a test device Verios 5 XHR SEM, and carrying out vacuum pumping for testing.
2. Raman sample preparation method
The materials were ground into powder, transferred to a glass stage, and then the stage was transferred to an in situ raman diffraction tester for raman spectroscopy.
3. XPS sample preparation method
(1) Clean In films (> 1cm X1 cm) were prepared.
(2) The sample was spread on an In film and the powder was spread evenly over the tape with a clean stainless steel sampling spoon, as thin as possible.
(3) Another piece of clean In film or clean weighing paper was taken to cover the sample with acetone.
(4) In film or clean weighing paper + sample was placed between two flat stainless steel die blocks and ready for compression.
(5) The stainless steel module or clean weighing paper + sample is placed on the platform of the tablet press, the stainless steel block is held against movement by the left hand, and the press column is screwed down clockwise by the right hand (above the press) to compress the module.
(6) The oil drain knob (knob in front of the press) is screwed clockwise, the right pressure bar is pulled, the pressure is increased to about 10MPa, and the pressure is kept for more than ten seconds.
(7) During pressure relief, the oil release knob is unscrewed anticlockwise, the compression column is unscrewed anticlockwise, and the stainless steel module and the sample are taken down from the tablet press.
(8) The In film covering the sample or clean weighing paper is removed, and the In film adhered with the sample is knocked down gently, so that the powder remained on the surface is knocked down.
(9) And cutting out an In film along the periphery of the pressed sample to prepare a pressed sample of-1 cm multiplied by 1cm, and then adhering the pressed sample to an XPS sample table by double-sided adhesive to be tested.
4. XRD test method
Grinding the prepared powder material, transferring to a glass sheet object stage, transferring to an X-ray diffractometer, and performing scanning test, wherein the scanning range is 10-80 degrees, and the scanning speed is 5 degrees/min.
5. ICP test method
The molecular formula of the pre-alkali-metallized material was determined using ICP detection and testing of actual cell performance, where ICP-AES is known collectively as inductively coupled plasma-atomic emission spectroscopy (Inductively Coupled Plasma-Atomic Emission Spectrometry), also known as inductively coupled plasma-emission spectroscopy (ICP-OES). The sample treatment process is as follows:
(1) Weighing: accurately weighing about 0.1g of sample in a 50ml polytetrafluoroethylene digestion tube, and recording the mass of the sample.
(2) To the weighed sample digestion tubes, an appropriate amount of mineral acid (typically 5ml of concentrated nitric acid/1 ml of hydrofluoric acid) was added, respectively. The lid was closed and placed in a stainless steel reaction kettle, and after heating in an oven at 190℃for about 10 hours, the heating and cooling was stopped.
(3) The cooled solution was transferred to a 25ml plastic volumetric flask and finally to volume with deionized water.
(4) Preparing a standard test solution, wherein the standard solution is a national standard substance, and the concentration points of the curve are respectively: 0. 0.5, 1.0, 2.0, 5.0mg/L;
(5) And (3) instrument testing, namely firstly preparing a standard solution calibration curve through an ICP-OES (inductively coupled plasma-optical emission spectrometry) instrument, inputting the mass and the volume of a sample, then sequentially testing the digested solution, and testing after dilution beyond the curve range.
(6) And determining the final content of the element to be tested in each sample through a spectrogram, and obtaining a test result.
6. Assembly and test of soft package battery core
The positive electrode material, the conductive carbon and the PVDF are weighed according to the mass ratio of 90:5:5, dissolved in a certain amount of NMP, stirred, coated, dried and cut into pieces. Then, the anode hard carbon material, the conductive carbon and CMC/SBR are weighed according to the mass ratio of 85:10:5, dissolved in a certain amount of water, stirred, coated, dried and cut into pieces. The pole piece adopts a winding process, the diaphragm is firstly wound for 5/6 circles, then the anode and the cathode are sequentially wound for 8 circles, and finally the anode is wound, so that the cathode piece is completely wrapped in the anode. The prepared winding core is welded with the tab and glued, then is sealed by an aluminum plastic film, is taken out after being baked for 40 to 120 hours in a vacuum oven, and is tested for water content (requirement H 2 O<200 ppm), and then injecting liquid according to a certain liquid injection coefficient and proportion, sealing, aging, forming and capacity-dividing testing. Wherein the electrolyte is 1M sodium hexafluorophosphate dissolved in the volume ratio EC: dec=1:1+5% fec in solvent.
The assembled battery is placed on a blue standard tester for 8 hours, and then starts to test, and is charged and discharged at a rate of 0.1C, wherein the theoretical specific capacity is 130/370mAh/g (the capacity is designed according to the pre-calculation). And charging and discharging at first by adopting a current of 0.1C, and finally, reading and calculating a corresponding capacity value.
Example 1: preparation of Li based on precursor salts 0.18 -GDY@NNFM
(1) And adding precursor salt of nickel hydroxide iron manganese and sodium carbonate into a reaction container according to the molar ratio of 1:0.535, and performing ball milling and stirring uniformly, wherein the ball milling rotating speed is 600 rpm, and the ball milling time is 2.4 hours. Solid sintering the mixture at 980 deg.c and temperature raising rate of 4.5 deg.c/min for 10.5 hr to obtain the final productTo NaNi 0.34 Fe 0.33 Mn 0.33 O 2 (NNFM) powder;
(2) Lithium carbide and hexachlorobenzene (C) were mixed in a molar ratio of 3:2 6 Cl 6 ) Placing the mixture in a vacuum ball milling tank, and adding 30mL of absolute ethyl alcohol; sealing the ball milling tank, vacuumizing the ball milling tank or introducing inert gas; ball milling by a planetary ball mill at a rate of 1000rpm for 6 hours; taking out the sample after ball milling, washing with deionized water for three times to remove unreacted impurities, and drying and grinding the sample at 90 ℃; washing for 6 times to remove the hexachlorobenzene which is not completely reacted; the obtained sample is uniformly spin-coated on a triethyl borate (TEB) membrane and dried at 90 ℃ to obtain Li 0.18 -GDY powder;
(3) Li is mixed with 0.18 The GDY powder and NNFM powder are evenly stirred and mixed, transferred to a high-energy ball mill for wet mixing, the solvent is ethanol, the rotating speed is 450rpm, and the time is 5 hours; drying at 90 ℃ to obtain Li 0.18 -gdy@nnfm powder.
Example 2: preparation of Li based on Metal salts 0.18 -GDY@NNFM
Example 2 differs from example 1 in that: the NNFM is prepared by taking sodium carbonate, nickel nitrate, ferrous oxalate and manganese oxide with the molar ratio of 0.535:0.34:0.33:0.33 as raw materials, and other steps are the same.
Example 3: preparation of Li 0.01 -GDY@NNFM
Example 3 differs from example 1 in that: the molar ratio of lithium carbide to hexachlorobenzene was 0.0142:0.01, and the amount of Li in the synthesized composite graphite alkyne was 0.01.
Example 4: preparation of Li-GDY@NNFM
Example 4 differs from example 1 in that: the molar ratio of lithium carbide to hexachlorobenzene was 1.55:1, and the amount of Li in the synthesized composite graphite alkyne was 1.
Example 5: preparation of Na 0.18 -GDY@NNFM
Example 5 differs from example 1 in that: li is replaced by Na, the molar ratio of sodium carbide to hexachlorobenzene is 3:2, and the amount of Na in the synthesized composite graphite alkyne is 0.18.
Example 6: preparation of K 0.18 -GDY@NNFM
Example 6 differs from example 1 in that: the molar ratio of potassium carbide to hexachlorobenzene is 3:2 by replacing Li with K, and the amount of K in the synthesized composite graphite alkyne is 0.18.
Example 7: preparation of K-GDY@NNFM
Example 7 differs from example 1 in that: the molar ratio of potassium carbide to hexachlorobenzene is 1.55:1 by replacing Li with K, and the amount of K in the synthesized composite graphite alkyne is 1.
Example 8: preparation of Na-GDY@NNFM
Example 8 differs from example 1 in that: li is replaced by Na, the molar ratio of sodium carbide to hexachlorobenzene is 1.55:1, and the amount of Na in the synthesized composite graphite alkyne is 1.
Example 9: preparation of Na 0.01 -GDY@NNFM
Example 9 differs from example 1 in that: li is replaced by Na, the molar ratio of sodium carbide to hexachlorobenzene is 0.0142:0.01, and the amount of Na in the synthesized composite graphite alkyne is 0.01.
Comparative example 1: preparation of NNFM
Comparative example 1 differs from example 1 in that: preparation of NaNi 0.34 Fe 0.33 Mn 0.33 O 2 。
Comparative example 2: preparation of GDY@NNFM
Comparative example 2 differs from example 1 in that: the amount of Li was 0.
1. Characterization of materials
NNFM and Li prepared in the following for example 1 0.18 -gdy@nnfm for characterization testing.
Table 1 shows ICP test results of NNFM materials. As can be seen from the results in the table, NNFM is prepared having the molecular formula NaNi 0.34 Fe 0.33 Mn 0.33 O 2 。
TABLE 1
FIG. 2 is Li 0.18 -GDY scanning electron microscope and Mapping. As is evident from the figuresIn this material, GDY and Li are mutually wrapped.
FIG. 3 is Li 0.18 -GDY. From the figure, it can be seen that characteristic peaks of Li exist in the energy spectrum, which indicate that Li element is bonded in the molecule of the graphite alkyne.
FIG. 4a and FIG. 4b are Li 0.18 Scanning electron microscope image of GDY@NNFM material, from which can be seen Li 0.18 The GDY@NNFM material is in a complex flocculent state. FIG. 4c is an SEM image of a cut surface of the material, from which Li is evident 0.18 GDY encapsulate the NNFM material with an interface between the two. FIG. 4d is a brief drawing of the section mapping, also confirming the situation shown in FIG. 4 c. FIG. 4e and FIG. 4f are transmission electron microscope diagrams of the material, wherein the crystal planes corresponding to the lattice fringes in the diagram are specific crystal plane structures of NNFM material, which shows that the NNFM material is doped with Li 0.18 GDY are uniformly coated.
FIG. 5 is Li 0.18 -a raman spectrum of GDY material. As can be seen from the figure, a characteristic peak of benzene ring appears in the Raman spectrum (1584 cm -1 ) And alkynyl characteristic peak (1931 cm) -1 And 2188cm -1 ) This corresponds well to the actual situation of GDY molecules. In addition, li 0.18 2188cm of the benzene ring in GDY -1 The peak position of the characteristic peak was shifted (the peak position of the characteristic peak of the benzene ring in pure GDY was 2217 cm) -1 ) It is presumed that the raman characteristic peak of the alkynyl group is shifted due to the Li bonded to the GDY molecule.
FIG. 6 is Li 0.18 X-ray photoelectron spectrum of GDY@NNFM material, in which GDY specific sp and sp do appear 2 Peak position, indicating that the material does contain Li 0.18 GDY material, both organically bonded.
FIG. 7 is Li 0.18 The XRD pattern of the GDY@NNFM material, with its characteristic peaks substantially conforming to the standard card for the O3 phase, demonstrates that the material is indeed an O3-NNFM material. The curve has a slight upward slope in the 10-20 interval, indicating that the material contains carbon, and the presence of GDY is laterally demonstrated. No distinct characteristic peak is seen in the figure, since the Li content is low.
2. Electrochemical performance test
Prepared as in example 1Li of preparation 0.18 -gdy@nnfm as positive electrode active material, the assembled sodium ion pouch cell achieved an initial specific capacity of about 140.5 mA h/g in the voltage interval of 2-4V; after 30/90/180/360 days of storage, the specific discharge capacity of the material is 139.4/130.2/128.5/120.7mA h/g respectively, the capacity retention rate is 85.9%, and the battery life is very excellent.
Li prepared in example 2 0.18 -gdy@nnfm as positive electrode active material, the assembled sodium ion pouch cell achieved an initial specific capacity of about 130.2mA h/g in the voltage interval of 2-4V; after 30/90/180/360 days of storage, the specific discharge capacity of the material is 128.4/119.2/112.8/109.4mA h/g, and the capacity retention rate is 84.02%. Slightly lower than example 1.
By contrast, with the NNFM positive electrode active material prepared in comparative example 1, the assembled sodium ion pouch cell achieved an initial specific capacity of about 116.3mA h/g over a voltage range of 2-4V; after 30/90/180/360 days of storage, the specific discharge capacity of the material is 112.87/101.6/99.5/89.1mA h/g, and the capacity retention rate is 76.61%. This indicates that there is a significant decrease in cell performance without the introduction of a graphite alkyne composite coating.
The test results of the other examples and comparative examples are shown in table 2.
TABLE 2
From the results in table 2, it can be seen that: in comparative example 1, pure layered oxide NNFM was used as the positive electrode material, and the obtained sodium ion battery had the lowest specific discharge capacity, first coulombic efficiency and specific volume after storage; in comparative example 2, after the layered oxide NNFM was coated with pure graphite alkyne, the specific discharge capacity, the first coulombic efficiency and the specific volume after storage of the battery were all improved.
In example 1, a composite graphite alkyne Li 0.18 After NNFM is coated by GDY, the existence of alkali metal in the composite graphite alkyne generates a pre-alkali metal effect, so that the energy density of the material can be improved, and the discharge of the battery is realizedThe indexes of specific capacity, initial coulombic efficiency and the like are all obviously superior to those of comparative example 2 adopting graphite alkyne to coat NNFM.
Similarly, in examples 2-9, the NNFM was coated with the composite graphite alkyne, and the specific discharge capacity, the first coulombic efficiency and the specific volume after storage of the battery were further improved compared to NNFM and pure graphite alkyne coated NNFM.
In conclusion, the invention carries out cladding modification on the layered oxide by introducing the alkali metal/graphite alkyne composite material, can greatly improve the energy density and the service life of the full battery, and well compensates the initial coulomb efficiency of the full battery loss.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A composite graphite alkyne modified layered oxide material is characterized in that the molecular formula of the composite graphite alkyne modified layered oxide material is M x -GDY@NaNi a Fe b Mn c O 2 Wherein: m is at least one of Li, na and K, x is more than or equal to 0.01 and less than or equal to 1; 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1.
2. The composite graphite alkyne-modified layered oxide material according to claim 1, wherein the composite graphite alkyne-modified layered oxide material has a D50 particle size of 0.01 to 100.5 μm;
and/or the specific surface area of the composite graphite alkyne modified layered oxide material is 0.01-16.9 m 2 /g。
3. The preparation method of the composite graphite alkyne modified layered oxide material is characterized by comprising the following steps of:
s1, under vacuum or inert atmosphere, hexahalobenzene and carbide M are reacted 2 C 2 Mixing with absolute ethanol, and making into ballGrind and wash to remove unreacted carbide M 2 C 2 The method comprises the steps of carrying out a first treatment on the surface of the Then, the ball-milling product is dried and ground at the temperature of 40-120 ℃, and then the unreacted hexahalobenzene is removed by washing; then, the ground product is dried at the temperature of 40 to 120 ℃ to obtain M x GDY powder, M is at least one of Li, na and K;
s2, M is x GDY powder, naNi a Fe b Mn c O 2 Mixing the powder, and performing wet ball milling; drying to obtain a composite graphite alkyne modified layered oxide material;
wherein in step S1, the carbide M 2 C 2 At least one of lithium carbide, sodium carbide and potassium carbide; x is more than or equal to 0.01 and less than or equal to 1;
in step S2, 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1.
4. The method for producing a composite graphite alkyne-modified layered oxide material according to claim 3, wherein in step S1, carbide M 2 C 2 The molar ratio of the benzene hexahalobenzene to the benzene hexahalobenzene is 1-18:1-6;
and/or removing unreacted carbide M by water washing 2 C 2 ；
And/or the rotating speed of the ball milling is 200-3000 rpm, and the ball milling time is 4-18 h.
5. The method for preparing a composite graphite alkyne-modified layered oxide material according to claim 3, wherein in step S2, the solvent for wet ball milling is ethanol;
and/or the rotating speed of the wet ball milling is 100-3000 rpm, and the time of the wet ball milling is 0.5-48 h;
and/or the temperature of the drying is 40-120 ℃.
6. The method for preparing a composite graphite alkyne-modified layered oxide material according to claim 3, wherein in step S2, the NaNi is a Fe b Mn c O 2 The preparation method of the powder comprises the following steps:
a. mixing sodium salt with metal salt, ball milling and stirring uniformly; the metal salt comprises at least one of nickel salt, iron salt and manganese salt;
b. sintering the mixture obtained in the step a at 800-1200 ℃ to obtain the NaNi a Fe b Mn c O 2 A powder;
wherein in the step a, the sodium salt comprises at least one of sodium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfide, sodium sulfite, sodium bisulphite, sodium nitrite, sodium chlorate, sodium ferrate, sodium fluoride, sodium bromide and sodium iodide;
and/or the nickel salt comprises at least one of nickel oxide, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide and nickel carbonyl;
and/or the ferric salt comprises at least one of ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate and ferrous oxalate;
and/or the manganese salt comprises at least one of manganese oxide, potassium permanganate and potassium manganate;
and/or the molar ratio of the sodium salt to the metal salt is 0.05-1.25:0.01-1.
7. The method for preparing a composite graphite alkyne-modified layered oxide material according to claim 3, wherein in step S2, the NaNi is a Fe b Mn c O 2 The preparation method of the powder comprises the following steps:
c. mixing sodium salt with precursor salt, ball milling and stirring uniformly;
d. sintering the mixture obtained in the step c at 800-1200 ℃ to obtain the NaNi a Fe b Mn c O 2 A powder;
wherein the sodium salt comprises at least one of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate;
and/or the precursor salt comprises at least one of nickel oxide, manganese oxide, iron oxide, nickel iron oxide, manganese iron oxide, nickel manganese oxide, nickel iron manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron hydroxide, manganese iron hydroxide, nickel manganese hydroxide and nickel iron manganese hydroxide;
and/or the molar ratio of the sodium salt to the precursor salt is 0.01-1.25:0.01-1.
8. The method for preparing a composite graphite alkyne-modified layered oxide material according to claim 6 or 7, wherein in steps a and c: the rotation speed of the ball milling is 100-1000 rpm, and the time of the ball milling is 0.2-3 h;
in steps b and d: the temperature rising rate of the sintering is 0.01-10 ℃/min, and the sintering time is 0.5-48 h.
9. A positive electrode sheet comprising the composite graphite alkyne-modified layered oxide material according to claim 1 or 2 or the composite graphite alkyne-modified layered oxide material prepared by the method according to any one of claims 3 to 8.
10. A sodium ion battery comprising the positive electrode sheet of claim 9.
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