CN116646501A - Negative electrode slurry for sodium ion battery - Google Patents
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- CN116646501A CN116646501A CN202310805022.4A CN202310805022A CN116646501A CN 116646501 A CN116646501 A CN 116646501A CN 202310805022 A CN202310805022 A CN 202310805022A CN 116646501 A CN116646501 A CN 116646501A
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- negative electrode
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- nitrogen
- sodium ion
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- 239000011267 electrode slurry Substances 0.000 title claims abstract description 32
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 31
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- 239000002028 Biomass Substances 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007833 carbon precursor Substances 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000009656 pre-carbonization Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- MJYQFWSXKFLTAY-OVEQLNGDSA-N (2r,3r)-2,3-bis[(4-hydroxy-3-methoxyphenyl)methyl]butane-1,4-diol;(2r,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O.C1=C(O)C(OC)=CC(C[C@@H](CO)[C@H](CO)CC=2C=C(OC)C(O)=CC=2)=C1 MJYQFWSXKFLTAY-OVEQLNGDSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 241000251468 Actinopterygii Species 0.000 claims description 3
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 235000004426 flaxseed Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 6
- 239000007773 negative electrode material Substances 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000007306 functionalization reaction Methods 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract description 2
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 241000758789 Juglans Species 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- -1 Polyethylene Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- OQUKGEUGTYTREP-UHFFFAOYSA-N copper iron(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Fe+2].[Cu+2].[Ni+2].[O-2].[O-2].[O-2] OQUKGEUGTYTREP-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides negative electrode slurry for sodium ion batteries, and relates to the technical field of sodium ion batteries. The negative electrode slurry for sodium ion battery comprises: modified hard carbon, conductive auxiliary materials, CMC, SBR and solvent, wherein the mass ratio of the modified hard carbon to the conductive auxiliary materials to the CMC to the SBR to the solvent is (8-10): (1-2): (0.1-0.3): (0.05-0.2): (0.03-0.15): (2-6), wherein the modified hard carbon is prepared by modifying nitrogen-phosphorus doped hard carbon. According to the negative electrode slurry, nitrogen and phosphorus doped hard carbon is adopted as a negative electrode material, the surface and functional group functionalization of the hard carbon negative electrode material are effectively improved through doping of nitrogen and phosphorus atoms, the electronic structure of a hard carbon bulk phase is effectively changed, the conductivity of the material is enhanced, more reversible defects and lithium ion reactive sites are introduced, and the interlayer spacing of a graphite-like structure is increased, so that a sodium battery can obtain larger capacity and stable cycle performance.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to negative electrode slurry for a sodium ion battery.
Background
Electricity can be used as both an energy source and an information carrier, and has profoundly affected almost all production and living activities of humans.
As an energy source, electric energy can come from clean renewable resources such as wind energy, solar energy, hydraulic potential energy of rivers and the like, relative to fossil energy with limited resources; the transport transfer performance has incomparable advantages of fossil energy and the like, and can be transmitted by a power system or even free space in a wireless way. Even in evaluating the human civilization level, the development and utilization capacity for electric energy represents a higher civilization level than the development capacity for fossil energy.
Currently humans face the double dilemma of fossil energy depletion and environmental pollution, so clean renewable energy must be developed to reduce the reliance on fossil energy. The secondary battery has high energy storage energy density, high conversion efficiency and high flexibility, and is one of the current research hotspots. The secondary batteries that are the most promising at present are mainly lithium ion batteries and sodium ion batteries. Among the existing battery energy storage, lithium ion batteries are currently a mature solution. However, the lithium battery has the problems that electrode materials are active, risks such as combustion and explosion are possibly caused, and the lithium battery is still limited by the limitation of energy density and has high storage cost as a large-capacity energy storage.
With the continued depth of research, the potential advantages of sodium ion batteries are continually explored. Particularly, the performance is excellent at high and low temperatures, and the safety is higher, thus laying a good foundation for the application of sodium ion batteries in the fields of energy storage and power. The existing sodium ion battery adopts hard carbon as a main negative pressure material, but the initial coulomb efficiency and the sodium storage capacity of the existing hard carbon material are not ideal enough, so that the sodium ion battery has low energy density, poor multiplying power performance and short cycle life.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides the negative electrode slurry for the sodium ion battery, and solves the problems of the existing hard carbon material that the initial coulomb efficiency and the sodium storage capacity are not ideal enough.
(II) technical scheme
In order to achieve the above purpose, the invention is realized by the following technical scheme: a negative electrode slurry for a sodium ion battery comprising: modified hard carbon, conductive auxiliary materials, CMC, SBR and solvent, wherein the mass ratio of the modified hard carbon to the conductive auxiliary materials to the CMC to the SBR to the solvent is (8-10): (0.05-0.2): (0.03-0.15): (2-6), wherein the modified hard carbon is prepared by modifying nitrogen-phosphorus doped hard carbon.
Preferably, the conductive auxiliary material is one or more of conductive carbon black, carbon nanotubes, graphene and graphene oxide.
Preferably, the particle size of the graphite is set to 7-10 mu m, and the specific surface area of the graphite is set to 10-14 square meters per gram.
Preferably, the diameter of the SBR is set to 120-160 nm, the molecular weight of the CMC is set to 300-350 kg/mol, and the substitution degree of the CMC is set to 0.6-0.8.
Preferably, the preparation method of the nitrogen-phosphorus doped hard carbon comprises the following steps:
crushing and sieving biomass with nitrogen element and phosphorus element content not lower than 0.3%, and repeatedly soaking and cleaning the biomass with ethanol solution to obtain high-purity particles;
step two, putting the high-purity particles into caustic soda solution, heating and stirring the high-purity particles for 2 to 3 hours, washing and drying the particles to obtain a biomass carbon precursor;
step three: adding nano hollow carbon spheres into the biomass carbon precursor, uniformly mixing, and then carrying out pre-carbonization treatment for 24 hours to obtain a pre-carbonized precursor;
step four: calcining the pre-carbonized precursor under the protection of nitrogen to obtain a hard carbon material;
step five: dissolving a hard carbon material in water, adding a composite carbon source, a nitrogen source and a phosphorus source while stirring, filtering, drying, and calcining at high temperature to obtain the nitrogen-phosphorus doped hard carbon.
Preferably, the biomass with the content of nitrogen element and phosphorus element not lower than 0.3% comprises flaxseed, walnut, shrimp shell, crab shell and deep sea fish biomass, the composite carbon source is one or more of graphite, soft carbon, graphene oxide and carbon nano tubes, and the mass ratio of the biomass carbon precursor to the nano hollow carbon spheres is 10: (1-2), wherein the mass ratio of the composite carbon source to the nitrogen source to the phosphorus source is 5: (3-6): (10-15).
Preferably, the modification treatment method of the nitrogen-phosphorus doped hard carbon comprises the following steps:
firstly, putting nitrogen-phosphorus doped hard carbon into an organic acid solution, and uniformly mixing;
step two, adopting a piezoelectric ultrasonic transducer to send out ultrasonic waves to carry out modification treatment on the mixed solution;
and thirdly, filtering and drying the mixed solution to obtain the modified nitrogen-phosphorus doped hard carbon.
Preferably, the organic acid is one of oxalic acid, malic acid, citric acid, benzoic acid and salicylic acid, and the ultrasonic frequency emitted by the piezoelectric ultrasonic transducer is set to be 15 kHz-20 MHz.
(III) beneficial effects
The invention provides a negative electrode slurry for a sodium ion battery. The beneficial effects are as follows:
1. according to the negative electrode slurry, nitrogen and phosphorus doped hard carbon is adopted as a negative electrode material, the surface and functional group functionalization of the hard carbon negative electrode material are effectively improved through doping of nitrogen and phosphorus atoms, the electronic structure of a hard carbon bulk phase is effectively changed, the conductivity of the material is enhanced, more reversible defects and lithium ion reaction active sites are introduced, the interlayer spacing of a graphite-like structure is increased, so that a sodium battery can obtain larger capacity and stable cycle performance, in addition, the hard carbon negative electrode material is compounded with a composite carbon source, the generation of side reaction can be relieved, and the first-circle coulomb efficiency of the hard carbon negative electrode material is improved.
2. The negative electrode slurry carries out surface treatment on the hard carbon, and introduces carbonyl and carboxyl of the organic acid into the hard carbon through ultrasonic waves, so that additional active centers and defects are provided for the hard carbon, the electron mobility is improved, and the sodium ion battery shows excellent multiplying power performance.
3. According to the negative electrode slurry, the nano hollow carbon spheres are added and pre-carbonization treatment is carried out during hard carbon processing, the nano hollow carbon spheres are broken after being mixed and carbonized with the hard carbon, so that the specific surface area of the hard carbon is increased, the structural order of a hard carbon material can be effectively improved through the pre-carbonization treatment, and the first-circle coulomb efficiency of a sodium ion battery can be effectively provided through the combination of the nano hollow carbon spheres and the hard carbon.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
the embodiment of the invention provides a negative electrode slurry for a sodium ion battery, which comprises the following components: modified hard carbon, conductive auxiliary materials, CMC, SBR and a solvent, wherein the mass ratio of the modified hard carbon to the conductive auxiliary materials to the CMC to the SBR to the solvent is 9:3:0.2:0.1:0.04:3, the modified hard carbon is prepared by modifying nitrogen-phosphorus doped hard carbon, the conductive auxiliary material is a mixture of carbon nano tubes and graphene, the mass ratio of the carbon nano tubes to the graphene is 1:2, the particle size of graphite is set to 7-10 mu m, the specific surface area of the graphite is set to 10-14 square meters per gram, the diameter of SBR is set to 120-160 nm, the molecular weight of CMC is set to 300-350 kg/mol, and the substitution degree of CMC is set to 0.6-0.8.
The preparation method of the nitrogen-phosphorus doped hard carbon comprises the following steps:
crushing biomass with nitrogen and phosphorus content not lower than 0.3%, wherein the biomass with nitrogen and phosphorus content not lower than 0.3% comprises flaxseed, walnut, shrimp shell, crab shell and deep sea fish biomass, sieving the crushed biomass, setting the sieving mesh to be 50-200 meshes, and repeatedly soaking and cleaning by using ethanol solution to obtain high-purity particles;
step two, putting the high-purity particles into caustic soda solution, heating and stirring the high-purity particles at 90-120 ℃ for 2-3 hours, washing and drying the particles to obtain a biomass carbon precursor;
step three: adding nano hollow carbon spheres into a biomass carbon precursor, wherein the diameter of each nano hollow carbon sphere is set to be 50-120 nm, and the mass ratio of the biomass carbon precursor to the nano hollow carbon spheres is 10:1.5, uniformly mixing and then carrying out pre-carbonization treatment for 24 hours to obtain a pre-carbonized precursor;
step four: calcining the precarbonated precursor under the protection of nitrogen, wherein the calcining is carried out to the temperature of 120-150 ℃ for 1-2 hours, the calcining is carried out continuously to the temperature of 400-650 ℃ for 1-2 hours, and finally the temperature is carried out to the temperature of 900-1300 ℃ for 1-6 hours, and the heating rate is 7-10 ℃/min, so as to obtain the hard carbon material;
step five: dissolving a hard carbon material in water, and adding a composite carbon source, a nitrogen source and a phosphorus source while stirring, wherein the composite carbon source is a mixture of carbon nanotubes and graphene oxide, and the mass ratio of the composite carbon source to the nitrogen source to the phosphorus source is 5:5: and 12, filtering, drying, and calcining at high temperature to obtain the nitrogen-phosphorus doped hard carbon.
The modification treatment method of the nitrogen-phosphorus doped hard carbon comprises the following steps:
firstly, putting nitrogen-phosphorus doped hard carbon into an organic acid solution, wherein the organic acid is one of litho acid, oxalic acid, malic acid, citric acid, benzoic acid and salicylic acid, and uniformly mixing;
step two, adopting a piezoelectric ultrasonic transducer to emit ultrasonic waves to carry out modification treatment on the mixed solution, wherein the ultrasonic frequency is set to be 15 kHz-20 MHz;
and thirdly, filtering and drying the mixed solution to obtain the modified nitrogen-phosphorus doped hard carbon.
And coating the negative electrode slurry on a metal substrate, drying and cutting to form a negative electrode plate A.
Embodiment two:
the embodiment of the present invention provides a negative electrode slurry for a sodium ion battery, which is different from embodiment 1 in that: the modified hard carbon of this example was not subjected to modification treatment.
And coating the negative electrode slurry on a metal substrate, drying and cutting to form a negative electrode plate B.
Embodiment III:
the embodiment of the present invention provides a negative electrode slurry for a sodium ion battery, which is different from embodiment 1 in that: this example changes nitrogen-phosphorus doped hard carbon to plain hard carbon.
And coating the negative electrode slurry on a metal substrate, drying and cutting to form a negative electrode plate C.
Embodiment four:
the embodiment of the present invention provides a negative electrode slurry for a sodium ion battery, which is different from embodiment 1 in that: according to the embodiment, the nano hollow carbon spheres are not added into the biomass charcoal precursor, the negative electrode slurry is coated on a metal substrate, and the negative electrode plate D is formed by drying and then cutting.
Fifth embodiment:
the embodiment of the present invention provides a negative electrode slurry for a sodium ion battery, which is different from embodiment 1 in that: in this example, graphite is not added to the components, and the negative electrode slurry is coated on a metal substrate, dried and cut to form a negative electrode sheet E.
Comparative example:
the comparative example of the present invention provides a negative electrode slurry for a sodium ion battery, comprising: modified hard carbon, conductive auxiliary materials, CMC, SBR and a solvent, wherein the mass ratio of the modified hard carbon to the conductive auxiliary materials to the CMC to the SBR to the solvent is 9:3:0.2:0.1:0.04:3. and coating the negative electrode slurry on a metal substrate, drying and cutting to form a negative electrode sheet F.
Sodium-containing copper-nickel-iron-manganese oxide is used as a positive electrode, a mixture of Ethylene Carbonate (EC), propylene Carbonate (PC) and diethyl carbonate (DEC) containing NaPF6 is used as an electrolyte, a Polyethylene (PE) porous polymer film with the surface coated with Al2O3 is used as a separation film, the method comprises the steps of respectively taking a negative electrode plate A, a negative electrode plate B, a negative electrode plate C, a negative electrode plate D, a negative electrode plate E and a negative electrode plate F as a negative electrode, manufacturing a button cell through different processes, carrying out experiments, charging a full cell to 4.48V or 3.95V at a constant current of 0.2 ℃ in an environment of 25 ℃, and then charging at a constant voltage; the data of the capacity and the initial charge efficiency obtained by the test at 0.2C constant current discharge to voltage 2V are shown in table 1:
TABLE 1
From the above, the sodium removal specific capacity (namely the total reversible specific capacity) of the battery at 0-2V can reach 318mAh/g, the first coulomb efficiency can reach 91%, the corresponding first discharge capacity is mAh/g, and the specific capacity retention rate of 1000-week cyclic charge is 96%.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A negative electrode slurry for a sodium ion battery, comprising: modified hard carbon, conductive auxiliary materials, CMC, SBR and solvent, wherein the mass ratio of the modified hard carbon to the conductive auxiliary materials to the CMC to the SBR to the solvent is (8-10): (0.05-0.2): (0.03-0.15): (2-6), wherein the modified hard carbon is prepared by modifying nitrogen-phosphorus doped hard carbon.
2. The negative electrode slurry for sodium ion battery according to claim 1, wherein: the conductive auxiliary material is one or more of conductive carbon black, carbon nano tubes, graphene and graphene oxide.
3. The negative electrode slurry for sodium ion battery according to claim 1, wherein: the particle size of the graphite is set to 7-10 mu m, and the specific surface area of the graphite is set to 10-14 square meters per gram.
4. The negative electrode slurry for sodium ion battery according to claim 1, wherein: the diameter of the SBR is set to be 120-160 nm, the molecular weight of the CMC is set to be 300-350 kg/mol, and the substitution degree of the CMC is set to be 0.6-0.8.
5. The negative electrode slurry for sodium ion battery according to claim 1, wherein: the preparation method of the nitrogen-phosphorus doped hard carbon comprises the following steps:
crushing and sieving biomass with nitrogen element and phosphorus element content not lower than 0.3%, and repeatedly soaking and cleaning the biomass with ethanol solution to obtain high-purity particles;
step two, putting the high-purity particles into caustic soda solution, heating and stirring the high-purity particles for 2 to 3 hours, washing and drying the particles to obtain a biomass carbon precursor;
step three: adding nano hollow carbon spheres into the biomass carbon precursor, uniformly mixing, and then carrying out pre-carbonization treatment for 24 hours to obtain a pre-carbonized precursor;
step four: calcining the pre-carbonized precursor under the protection of nitrogen to obtain a hard carbon material;
step five: dissolving a hard carbon material in water, adding a composite carbon source, a nitrogen source and a phosphorus source while stirring, filtering, drying, and calcining at high temperature to obtain the nitrogen-phosphorus doped hard carbon.
6. The negative electrode slurry for sodium ion battery according to claim 5, wherein: the biomass with the nitrogen element and phosphorus element content not lower than 0.3% comprises flaxseed, walnut, shrimp shell, crab shell and deep sea fish biomass, the composite carbon source is one or more of graphite, soft carbon, graphene oxide and carbon nanotubes, and the mass ratio of the biomass carbon precursor to the nano hollow carbon spheres is 10: (1-2), wherein the mass ratio of the composite carbon source to the nitrogen source to the phosphorus source is 5: (3-6): (10-15).
7. The negative electrode slurry for sodium ion battery according to claim 1, wherein: the method for modifying the nitrogen-phosphorus doped hard carbon comprises the following steps:
firstly, putting nitrogen-phosphorus doped hard carbon into an organic acid solution, and uniformly mixing;
step two, adopting a piezoelectric ultrasonic transducer to send out ultrasonic waves to carry out modification treatment on the mixed solution;
and thirdly, filtering and drying the mixed solution to obtain the modified nitrogen-phosphorus doped hard carbon.
8. The negative electrode slurry for sodium ion battery according to claim 1, wherein: the organic acid is one of lithoid, oxalic acid, malic acid, citric acid, benzoic acid and salicylic acid, and the ultrasonic frequency emitted by the piezoelectric ultrasonic transducer is set to be 15 kHz-20 MHz.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116924389A (en) * | 2023-08-30 | 2023-10-24 | 北京航空航天大学 | Hard carbon, preparation method thereof and sodium ion battery prepared from hard carbon |
| CN117393738A (en) * | 2023-12-01 | 2024-01-12 | 山西华钠碳能科技有限责任公司 | Negative electrode material and preparation method thereof |
| CN118461309A (en) * | 2024-07-09 | 2024-08-09 | 临沂大学 | Preparation method of carbon-based negative electrode material for sodium ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116924389A (en) * | 2023-08-30 | 2023-10-24 | 北京航空航天大学 | Hard carbon, preparation method thereof and sodium ion battery prepared from hard carbon |
| CN116924389B (en) * | 2023-08-30 | 2024-03-15 | 北京航空航天大学 | Hard carbon, preparation method thereof and sodium ion battery prepared from hard carbon |
| CN117393738A (en) * | 2023-12-01 | 2024-01-12 | 山西华钠碳能科技有限责任公司 | Negative electrode material and preparation method thereof |
| CN117393738B (en) * | 2023-12-01 | 2024-04-26 | 山西华钠碳能科技有限责任公司 | Negative electrode material and preparation method thereof |
| CN118461309A (en) * | 2024-07-09 | 2024-08-09 | 临沂大学 | Preparation method of carbon-based negative electrode material for sodium ion battery |
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