CN117566814A - Quaternary precursor for sodium electricity and preparation method thereof - Google Patents
Quaternary precursor for sodium electricity and preparation method thereof Download PDFInfo
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- CN117566814A CN117566814A CN202311617516.6A CN202311617516A CN117566814A CN 117566814 A CN117566814 A CN 117566814A CN 202311617516 A CN202311617516 A CN 202311617516A CN 117566814 A CN117566814 A CN 117566814A
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- 239000002243 precursor Substances 0.000 title claims abstract description 69
- 239000011734 sodium Substances 0.000 title claims abstract description 32
- 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 title claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 22
- 230000005611 electricity Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000012716 precipitator Substances 0.000 claims abstract description 13
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 3
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 3
- 238000005253 cladding Methods 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000013461 design Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- CIWBSHSKHKDKBQ-SZSCBOSDSA-N 2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one Chemical compound OC[C@H](O)C1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-SZSCBOSDSA-N 0.000 claims description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- 239000002211 L-ascorbic acid Substances 0.000 claims description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- 235000006708 antioxidants Nutrition 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 230000008602 contraction Effects 0.000 abstract description 2
- 230000008595 infiltration Effects 0.000 abstract description 2
- 238000001764 infiltration Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 239000011572 manganese Substances 0.000 description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000011701 zinc Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 125000004122 cyclic group Chemical group 0.000 description 10
- 238000005245 sintering Methods 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JOUIQRNQJGXQDC-AXTSPUMRSA-N namn Chemical compound O1[C@@H](COP(O)([O-])=O)[C@H](O)[C@@H](O)[C@@H]1[N+]1=CC=CC(C(O)=O)=C1 JOUIQRNQJGXQDC-AXTSPUMRSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003746 yttrium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of sodium ion battery anode materials, and particularly relates to a quaternary precursor for sodium electricity and a preparation method thereof; the main element of the quaternary precursor is Ni, fe, mn, zn, and the doping or cladding element is one of Y, ti and Cr; the quaternary precursor is prepared by a coprecipitation method and is matched with an antioxidant, a complexing agent and a precipitator, and the molecular formula of the quaternary precursor is Ni 0.22 Fe 0.33 Mn 0.33 Zn m X n (OH) 2 Wherein m+n=0.12, m is not less than 0.06, n is not less than 0, X is one of Y, ti and Cr; the quaternary precursor for sodium electricity is easy to fire single crystals, and single crystal materials are not easy to crack in the expansion and contraction of crystal grains, so that the reaction caused by the infiltration of electrolyte into the crystal grains can be well avoided; the fired monocrystalline material has round shape, uniform granularity, less agglomeration and easy gas breakage; the precursor of the element proportioning combination can effectively reduce lattice distortion caused by Mn < 3+ > and enhance the combination between M and O, so that the material has better high-rate cycle performance.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery anode materials, and particularly relates to a quaternary precursor for sodium electricity and a preparation method thereof.
Background
In recent years, a layered oxide positive electrode material (Na x MO 2 M represents a transition metal) has become a hotspot for sodium-electricity research, and the preparation method mainly comprises a solid phase method, a sol-gel method, a coprecipitation method and the like. The coprecipitation method can obtain a precursor with specific physical and chemical properties by controlling reaction conditions, and the prepared positive electrode material has smooth surface, uniform particle size distribution and higher tap density, and is a method suitable for industrial production. The coprecipitation method is also a mainstream method for producing lithium battery precursors, and inherits the existing equipment and process foundation of lithium batteries, and is the advantage of rapid industrialization of sodium batteries.
At present, a unified consensus is not formed on physical and chemical characteristics, proportion content and element combination of a sodium-electricity layered oxide precursor. The precursor with various physicochemical properties and element combinations is prepared by various manufacturers around capacity, circulation improvement, rate capability improvement, reduction of electrolyte side reaction and the like. For example, patent CN114291852A discloses a nickel-aluminum coated nickel-iron-manganese precursor Ni for solving the problem of water sensitivity of sodium ion battery and reducing side reaction of electrolyte 0.35 Fe 0.32 Mn 0.32 Al 0.01 (OH) 2 Combining the precursor with Na 2 CO 3 After mixing, sintering is carried out for 20 hours at 850 ℃, and the obtained positive electrode material has better constant-current capacity retention rate, but the capacity is lower, and the cycle performance characterization under high multiplying power is lacking. In order to solve the problem of side reaction of electrode material and electrolyte, the patent CN109817970A firstly synthesizes a battery-grade hydroxide precursor by a coprecipitation method, and prepares Na (Fe) by sintering in air atmosphere 1-x-a Mn x M a ) O2 (M is Ni)Cu, mg, co, cr, ti, al) and the like, and the capacity of the single crystal material reaches 121mAh/g at a low rate. In order to improve the circulation performance, for example, patent CN114644361A is prepared into NaMn by a coprecipitation method matched with a sintering process at 850 DEG C 0.50 Ni 0.28 Co 0.19 Ti 0.03 O 2 The capacity was 115.2mAh/g at 1C, and the capacity retention at 200 weeks of 1C cycle was 62.7%.
The above patent does not explain the preparation method, and the precursors of the structure and the element proportion can promote circulation, and the technical principles applied by the precursors are basically consistent through analysis. The precursor is coated, so that interface reaction between the positive electrode active material and electrolyte after sintering is reduced, the electrolyte inert element is preferably selected for coating, and the influence on ion transmission and electron conduction after coating is small. In addition, the precursor is doped so as to reduce lattice distortion, reduce structural damage after frequent phase change in the charge and discharge process, and the like. There is still a wide room for improvement in precursor optimization based thereon.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a quaternary precursor for sodium electricity and a preparation method thereof, which can reduce the interface reaction between a positive electrode material and electrolyte and reduce the sodium ion transmission barrier so as to improve the high-rate cycle performance of the material while considering the sodium capacitance.
The purpose of the invention is realized in the following way: a quaternary precursor for sodium electricity, wherein the main element of the quaternary precursor is Ni, fe, mn, zn, and the doping or cladding element is one of Y, ti and Cr; the quaternary precursor is prepared by a coprecipitation method and is matched with an antioxidant, a complexing agent and a precipitator, and the molecular formula of the quaternary precursor is Ni 0.22 Fe 0.33 Mn 0.33 Zn m X n (OH) 2 Wherein m+n=0.12, m is greater than or equal to 0.06, n is greater than or equal to 0, and X is one of Y, ti and Cr.
The preparation method of the quaternary precursor for sodium electricity comprises the following steps:
step 1: preparing Ni, fe, mn, zn mixed salt solution by pure water in a closed stirring tank according to a designed proportion, adding L (+) -ascorbic acid into the mixed salt solution according to 0.01-0.1% of the total mass of the mixed salt, and finally preparing salt (1); then, independently preparing one of Y, ti and Cr into a salt solution with the concentration of 0.1-0.5mol/L, and marking the salt solution as salt (2);
step 2: preparing an alkali solution with the concentration of 4-8 mol/L as a precipitator (1); diluting ammonia water into a solution with the concentration of 4-8 mol/L, preparing trisodium citrate into a solution with the concentration of 1-2 mol/L, and respectively marking the solution as a complexing agent (1) and a complexing agent (2);
step 3: injecting a certain amount of pure water into the reaction kettle, stirring, heating, and then bubbling N with purity more than or equal to 99.9% into the kettle 2 The nitrogen is blown into the salt (1) and the precipitant (1) at the same time;
step 4: adding a precipitator (1) into the kettle after nitrogen is blown for 2 hours, and adding a complexing agent (1) and a complexing agent (2) into the kettle;
step 5: setting the flow of the salt (1) and the flow of the precipitant and the flow of the complexing agent in the step (4) according to the process requirements, uniformly pumping the reagent into a reaction kettle through a metering pump for synthesis reaction, and keeping the temperature and the stirring speed in the step (3) in the reaction kettle;
step 6: slowly lowering the PH to 11.0-11.4 during 4-10 hours of the reaction, then keeping the ph=11.0-11.4 for further reaction for 48 hours; in the reaction process, the solid content of the reaction kettle is increased through a concentrator, the clear flow rate of the concentrator is 2-5L/h, and nitrogen is introduced into the concentrator to keep micro positive pressure;
step 7: after 48 hours of reaction, switching the salt (1) into a salt (2) with a set flow rate; simultaneously, the flow rate of the precipitator (1) is reduced to maintain the PH in the step 6 in the kettle, and the flow rates of the complexing agents (1) and (2) are reduced to maintain the concentration of the complexing agent in the step 4; the reaction is kept until the coating amount of the salt (2) reaches the design requirement; finally, reducing the stirring rotation speed, and keeping the temperature at constant temperature to obtain the required precursor slurry;
step 8: pumping the slurry in the step 7 into a centrifugal machine for filtering, and washing a filter cake by 0.5-2mol/L of dilute alkali and 50-70 ℃ of hot pure water; then carrying out dynamic drying, sieving, demagnetizing and other treatments to finally obtain a precursor finished product Ni 0.22 Fe 0.33 Mn 0.33 Zn m X n (OH) 2 (m+n＝0.12，m≥0.06，n≥0)；
Step 9: the precursor finished product in the step 8 and Na 2 CO 3 Placing the materials into a mixer for uniform mixing; placing the mixed materials in an atmosphere furnace, and preserving heat; grinding, gas breaking, screening and the like after cooling to obtain a positive electrode material NaNi 0.22 Fe 0.33 Mn 0.33 Zn m X n O 2 。
Preferably, the mixed salt solution of Ni, fe, mn, zn formulated in step 1 has an amount concentration of 1.5 to 2.0mol/L of substance.
Preferably, the salt (1) in the step 1 is soluble salt with the total concentration of 1.5-2mol/L and comprises the raw material NiSO 4 ·6H 2 O、MnSO 4 ·H 2 O、FeSO 4 ·7H 2 O、ZnSO 4 ·7H 2 O; the salt (2) is Y 2 (SO 4 ) 3 ·8H 2 O、TiCl 4 、Cr 2 (SO 4 ) 3 ·6H 2 One of the O is a soluble salt of 0.1-0.5 mol/L.
Preferably, the precipitant (1) in the step 2 is prepared by diluting 32% aqueous alkali with pure water; the complexing agent (1) is prepared by diluting 20% ammonia water, and the complexing agent (2) is prepared by Na 3 C 6 H 5 O 7 ·2H 2 O is dissolved in pure water.
Preferably, the stirring speed in the step 3 is 600-900 rpm, and the temperature is raised to 45-65 ℃.
Preferably, in the step 4, after nitrogen is blown in for 2 hours, adding the precipitator (1) into the kettle until the PH=11.7-12.1 of the bottom water, and adding the complexing agent (1) and the complexing agent (2) into the kettle until the concentration of the two complexing agents in the bottom water is respectively 4-10g/L and 0.01-0.1mol/L; in the step 5, the pH and complexing agent concentrations described in the step 4 are maintained at the beginning of the synthesis reaction.
Preferably, in the step 6, nitrogen is introduced into the thickener to maintain the micro positive pressure of 0.02-0.04Mpa.
Preferably, in the step 7, the stirring rotation speed is reduced to 300-500rpm, and the required precursor slurry is obtained after constant temperature maintenance for 2 hours.
Preferably, in the step 9, the precursor is formedProduct and Na 2 CO 3 Placing the materials into a mixer in a proportion of 1:1-1:1.07 for uniform mixing; placing the mixed materials into an atmosphere furnace, and preserving the temperature for 12-24 hours at 850-1000 ℃.
The quaternary precursor for sodium electricity has the following beneficial effects:
1. the monocrystal is easy to fire, and the monocrystal material is not easy to crack during the expansion and contraction of the crystal grains, so that the reaction caused by the infiltration of electrolyte into the crystal grains can be well avoided.
2. The fired monocrystalline material has round shape, uniform granularity, less agglomeration and easy gas breakage. These properties on the one hand greatly improve the recycling properties of the material and on the other hand are easy to process during production, so that the production costs and the equipment costs are reduced.
3. The precursor of the element proportioning combination can effectively reduce lattice distortion caused by Mn < 3+ > and enhance the combination between M and O, so that the material has better high-rate cycle performance.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
Fig. 1 is an SEM topography of the precursor of example 1 of the present invention.
Fig. 2 is an XRD pattern of the precursor in example 1 of the present invention.
Fig. 3 is an SEM morphology of the positive electrode in example 1 of the present invention.
Fig. 4 is an XRD pattern of the positive electrode in example 1 of the present invention.
Fig. 5 is a cycle test chart in embodiment 1 of the present invention.
Fig. 6 is an SEM topography of the precursor in example 2 of the present invention.
Fig. 7 is an SEM morphology of the positive electrode in example 2 of the present invention.
Fig. 8 is a cycle test chart in embodiment 2 of the present invention.
Fig. 9 is an SEM topography of the precursor in example 3 of the present invention.
Fig. 10 is an SEM morphology of the positive electrode in example 3 of the present invention.
Fig. 11 is a cycle test chart in embodiment 3 of the present invention.
FIG. 12 is a SEM topography of example 4 of the invention with a precursor Y-ratio of 0.
Fig. 13 is an SEM morphology of example 4 of the present invention with a precursor Y ratio of 0.02.
Fig. 14 is an SEM morphology of precursor Y with a ratio of 0.06 in example 4 of the present invention.
Fig. 15 is an SEM morphology of example 4 with positive electrode Y ratio of 0.
FIG. 16 is a SEM topography of example 4 of the invention with a positive Y-ratio of 0.02.
Fig. 17 is an SEM morphology of example 4 with a positive electrode Y ratio of 0.06.
FIG. 18 is a diagram of Ni in example 4 of the present invention 0.22 Fe 0.33 Mn 0.33 Zn 0.12 (OH) 2 Is a cyclic test chart of (c).
FIG. 19 is a diagram of Ni in example 4 of the present invention 0.22 Fe 0.33 Mn 0.33 Zn 0.1 Y 0.02 (OH) 2 Is a cyclic test chart of (c).
FIG. 20 is a diagram of Ni in example 4 of the present invention 0.22 Fe 0.33 Mn 0.33 Zn 0.06 Y 0.06 (OH) 2 Is a cyclic test chart of (c).
FIG. 21 is a cycle test chart in comparative example 1 of the present invention.
FIG. 22 shows NaNi of comparative example 2 of the present invention 0.22 Fe 0.33 Mn 0.33 Zn 0.08 Y 0.04 O 2 Is a cyclic test chart of (c).
FIG. 23 shows NaNi of comparative example 2 of the present invention 0.25 Fe 0.375 Mn 0.375 O 2 Is a cyclic test chart of (c).
FIG. 24 is a drawing of NaNi in comparative example 3 of the present invention 0.22 Fe 0.33 Mn 0.33 Zn 0.08 Y 0.04 O 2 Is a cyclic test chart of (c).
FIG. 25 shows NaNi in comparative example 3 of the present invention 0.25 Fe 0.375 Mn 0.375 O 2 Is a cyclic test chart of (c).
Detailed Description
The invention is further described below with reference to the accompanying drawings.
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The following description of the technical solutions in the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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.
Example 1
1) According to the design proportion of Ni to Fe to Mn to Zn, Y=0.22:0.33:0.33:0.08:0.04, preparing nickel, iron, manganese and zinc quaternary mixed salt with the total metal concentration of 1.85M by pure water in a closed stirring tank, and adding L (+) -ascorbic acid into the mixed salt solution according to 0.025 percent of the total mass of the mixed salt solution to finally prepare the salt (1) ". The yttrium salt of 0.25M was designated as "salt (2)".
2) The NaOH solution was diluted with pure water to a basic solution with a concentration of 8M as "precipitant (1)". Diluting ammonia water into 8M solution, and preparing trisodium citrate into 2M solution, which are respectively marked as complexing agents (1) and (2);
3) Injecting a certain amount of pure water into the reaction kettle, starting stirring at 800rpm, heating to 65 ℃, and then blowing N with purity more than or equal to 99.9% into the kettle 2 The nitrogen gas was also blown into the gas, "salt (1)", and "precipitant (1)".
4) After nitrogen is blown into the kettle for 2 hours, adding a precipitator (1) into the kettle until the pH=12.0 of the bottom water, and adding a complexing agent (1) and a complexing agent (2) into the kettle until the concentration of the two complexing agents in the bottom water is 8g/L and 0.02mol/L respectively.
5) Setting the flow rate of salt (1) at 50ml/min, the flow rate of precipitant (1) at 18.5ml/min, the flow rate of complexing agent (1) at 6.4ml/min and the flow rate of complexing agent (2) at 1.5ml/min, uniformly pumping into a reaction kettle through a metering pump to carry out synthesis reaction, and keeping the temperature and stirring in the reaction kettle at the temperature of 3. The flow of the precipitant (1) and the flow of the complexing agents (1) and (2) are finely adjusted at the initial stage of the reaction, so that the PH and the concentration of the complexing agents in the kettle (4) are maintained.
6) The PH was slowly lowered to 11.2 during 4-10h of the reaction, and then the reaction was continued for 48h while maintaining ph=11.2. In the reaction process, the solid content of the reaction kettle is increased by a concentrator, the clear flow rate of the concentrator is 4L/h, and nitrogen is introduced into the concentrator to keep the micro-positive pressure (0.02-0.04 Mpa).
7) After 48 hours of reaction, the "salt (1)" was changed to "salt (2)", and the flow rate was set at 50ml/min. Simultaneously, the flow rate of the precipitator (1) is reduced to 3+/-1 ml/min to keep the PH in the kettle in the step of 6 ', and the flow rates of the complexing agents (1) and (2) are respectively reduced to 5+/-0.5 ml/min and 1.2+/-0.2 ml/min to keep the concentration of the complexing agent in the step of 4'. Continuing to react until the coating amount of the salt (2) reaches the design proportion requirement. And finally, reducing the stirring rotation speed to 500rpm, and keeping the temperature for 2 hours to obtain the required precursor slurry.
8) The slurry in "7)" was pumped into a centrifuge for filtration, and the cake was washed with 0.5-2mol/L of dilute alkali and 50-70℃of hot pure water. Then carrying out dynamic drying, sieving, demagnetizing and other treatments to finally obtain a precursor finished product Ni 0.22 Fe 0.33 Mn 0.33 Zn 0.08 Y 0.04 (OH) 2 The shape and peak form are shown in figures 1-4
9) Precursor finished product in "8)" and Na 2 CO 3 Placing the materials into a mixer in a ratio of 1:1.05 for uniform mixing. The mixed materials are placed in an atmosphere furnace and are kept at 930 ℃ for 12 hours. Grinding, gas breaking, screening and the like after cooling to obtain a positive electrode material NaNi 0.22 Fe 0.33 Mn 0.33 Zn 0.08 Y 0.04 O 2 . The morphology and peak shape are shown in figures 1-4.
And (3) detection: taking the positive electrode finished product in 9 and PVDF glue solutionThe SP powder conductive agent, NMP dispersant were mixed in a homogenizer as an active material slurry. Coating the slurry on an aluminum foil, drying and cutting into positive pole pieces with the diameter of 12 mm. Then glass fiber is taken as a diaphragm, DMC, EMC, EC, naPF with a certain mole ratio is adopted 6 The FEC mixed solution was used as an electrolyte, and a sodium sheet with a diameter of 15.6mm was used as a negative electrode to prepare a 2032 type button cell. The produced buckling electricity is placed in a blue electric testing system for electrochemical testing, charging and discharging voltage is selected to be 2.0-4.0V, testing temperature is 25 ℃, the buckling electricity is firstly circulated for two weeks at multiplying power of 0.1C, and then circulated for 3 weeks at multiplying power of 0.5C, 1C, 2C and 3C respectively. The cycle test is shown in figure 5.
Example 2:
prepared as in example 1 substituting Y in step "1") with Ti. Precursor Ni 0.22 Fe 0.33 Mn 0.33 Zn 0.08 Ti 0.04 (OH) 2 The morphology of the anode material is shown in figure 6, the morphology of the cathode material is shown in figure 7, and the cyclic test is shown in figure 8.
Example 3:
prepared as in example 1, substituting Cr for Y in step "1"). Precursor Ni 0.22 Fe 0.33 Mn 0.33 Zn 0.08 Cr 0.04 (OH) 2 The morphology of the positive electrode material is shown in figure 9, the morphology of the positive electrode material is shown in figure 10, and the cyclic test is shown in figure 11.
Example 4:
prepared as in example 1, the Y ratio in step "1" was configured to be 0, 0.02, 0.06, respectively. The prepared precursors are Ni respectively 0.22 Fe 0.33 Mn 0.33 Zn 0.12 (OH) 2 、Ni 0.22 Fe 0.33 Mn 0.33 Zn 0.1 Y 0.02 (OH) 2 、Ni 0.22 Fe 0.33 Mn 0.33 Zn 0.06 Y 0.06 (OH) 2 The precursor is shown in fig. 12-14, the shape of the positive electrode material is shown in fig. 15-17, and the cyclic test is shown in fig. 18-20.
Comparative example 1:
prepared as in example 1, zn and Y in step "1" were rejected. The prepared front partThe precursor is Ni 0.25 Fe 0.375 Mn 0.375 (OH) 2 The fired positive electrode material was tested for buckling as shown in fig. 21.
Comparative example 2:
preparation of NaNi with better electrochemical properties in example 1 by following the method in patent CN109817970A 0.22 Fe 0.33 Mn 0.33 Zn 0.08 Y 0.04 O 2 And NaNi having poor electrochemical properties in comparative example 1 0.25 Fe 0.375 Mn 0.375 O 2 A material. The cycle performance of the two materials is shown in figures 22-23.
Comparative example 3:
preparation of NaNi with better electrochemical properties in example 1 by following the method in patent CN114644361A 0.22 Fe 0.33 Mn 0.33 Zn 0.08 Y 0.04 O 2 And NaNi having poor electrochemical properties in comparative example 1 0.25 Fe 0.375 Mn 0.375 O 2 A material. The cycle performance of the two materials is shown in figures 24-25.
The first effect, 3C capacity, and cycle performance were all better in example 1, as can be seen from FIGS. 1-25. The performance of coating/doping yttrium is superior to that of coating/doping other elements; the material performance is superior to other ratios when the ratio of zinc to yttrium element is 0.08:0.04; the electrochemical performance of coating/doping without zinc as a precursor of the main element and without other elements is poor. The electrochemical properties after sintering of the precursor produced by the preparation method in the prior patent can be weaker than those of the examples, especially in terms of specific capacity. The statistical results are shown in Table 1.
Table 1: examples and comparative examples critical data
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The quaternary precursor for sodium electricity is characterized in that the main element of the quaternary precursor is Ni, fe, mn, zn, and the doping or cladding element is one of Y, ti and Cr; the quaternary precursor is prepared by a coprecipitation method and is matched with an antioxidant, a complexing agent and a precipitator, and the molecular formula of the quaternary precursor is Ni 0.22 Fe 0.33 Mn 0.33 Zn m X n (OH) 2 Wherein m+n=0.12, m is greater than or equal to 0.06, n is greater than or equal to 0, and X is one of Y, ti and Cr.
2. The method for preparing a quaternary precursor for sodium electricity according to claim 1, comprising the steps of:
step 1: preparing Ni, fe, mn, zn mixed salt solution by pure water in a closed stirring tank according to a design proportion, adding L (+) -ascorbic acid into the mixed salt solution according to 0.01% -0.1% of the total mass of the mixed salt, and finally preparing salt (1); then, independently preparing one of Y, ti and Cr into a salt solution with the concentration of 0.1-0.5mol/L, and marking the salt solution as salt (2);
step 2: preparing an alkali solution with the concentration of 4-8 mol/L as a precipitator (1); diluting ammonia water into a solution with the concentration of 4-8 mol/L, preparing trisodium citrate into a solution with the concentration of 1-2 mol/L, and respectively marking the solution as a complexing agent (1) and a complexing agent (2);
step 3: injecting a certain amount of pure water into the reaction kettle, stirring, heating, and then bubbling N with purity more than or equal to 99.9% into the kettle 2 The nitrogen is blown into the salt (1) and the precipitant (1) at the same time;
step 4: adding a precipitator (1) into the kettle after nitrogen is blown for 2 hours, and adding a complexing agent (1) and a complexing agent (2) into the kettle;
step 5: setting the flow of the salt (1) and the flow of the precipitant and the flow of the complexing agent in the step (4) according to the process requirements, uniformly pumping the reagent into a reaction kettle through a metering pump for synthesis reaction, and keeping the temperature and the stirring speed in the step (3) in the reaction kettle;
step 6: slowly lowering the PH to 11.0-11.4 during 4-10 hours of the reaction, then keeping the ph=11.0-11.4 for further reaction for 48 hours; in the reaction process, the solid content of the reaction kettle is increased through a concentrator, the clear flow rate of the concentrator is 2-5L/h, and nitrogen is introduced into the concentrator to keep micro positive pressure;
step 7: after 48 hours of reaction, switching the salt (1) into a salt (2) with a set flow rate; simultaneously, the flow rate of the precipitator (1) is reduced to maintain the PH in the step 6 in the kettle, and the flow rates of the complexing agents (1) and (2) are reduced to maintain the concentration of the complexing agent in the step 4; the reaction is kept until the coating amount of the salt (2) reaches the design requirement; finally, reducing the stirring rotation speed, and keeping the temperature at constant temperature to obtain the required precursor slurry;
step 8: pumping the slurry in the step 7 into a centrifugal machine for filtering, and washing a filter cake by 0.5-2mol/L of dilute alkali and 50-70 ℃ of hot pure water; then carrying out dynamic drying, sieving, demagnetizing and other treatments to finally obtain a precursor finished product Ni 0.22 Fe 0.33 Mn 0.33 Zn m X n (OH) 2 (m+n=0.12，m≥0.06，n≥0)；
Step 9: the precursor finished product in the step 8 and Na 2 CO 3 Placing the materials into a mixer for uniform mixing; placing the mixed materials in an atmosphere furnace, and preserving heat; grinding, gas breaking, screening and the like after cooling to obtain a positive electrode material NaNi 0.22 Fe 0.33 Mn 0.33 Zn m X n O 2 。
3. The method for preparing a quaternary precursor for sodium electricity according to claim 2, wherein the mass concentration of the mixed salt solution of Ni, fe, mn, zn prepared in the step 1 is 1.5-2.0mol/L.
4. The method for preparing a quaternary precursor for sodium electricity according to claim 3, wherein the salt (1) in the step 1 is a soluble salt with a total concentration of 1.5-2mol/L, and comprises the raw materialsNiSO material 4 ·6H 2 O、MnSO 4 ·H 2 O 、FeSO 4 ·7H 2 O、ZnSO 4 ·7H 2 O; the salt (2) is Y 2 (SO 4 ) 3 ·8H 2 O、TiCl 4 、Cr 2 (SO 4 ) 3 ·6H 2 One of the O is a soluble salt of 0.1-0.5 mol/L.
5. The method for preparing a quaternary precursor for sodium electricity according to claim 2, wherein the precipitant (1) in the step 2 is prepared by diluting 32% aqueous alkali with pure water; the complexing agent (1) is prepared by diluting 20% ammonia water, and the complexing agent (2) is prepared by Na 3 C 6 H 5 O 7 ·2H 2 O is dissolved in pure water.
6. The method for preparing a quaternary precursor for sodium electricity according to claim 2, wherein the stirring speed in the step 3 is 600-900 rpm, and the temperature is raised to 45-65 ℃.
7. The method for preparing a quaternary precursor for sodium electricity according to claim 6, wherein in the step 4, after nitrogen is blown in for 2 hours, a precipitator (1) is added into the kettle until the pH of bottom water is=11.7-12.1, and a complexing agent (1) and a complexing agent (2) are added into the kettle until the concentration of the two complexing agents in the bottom water is 4-10g/L and 0.01-0.1mol/L respectively; in the step 5, the pH and complexing agent concentrations described in the step 4 are maintained at the beginning of the synthesis reaction.
8. The method for preparing a quaternary precursor for sodium electricity according to claim 2, wherein in the step 6, nitrogen is introduced into the concentrator to maintain micro positive pressure of 0.02-0.04Mpa.
9. The method for preparing a quaternary precursor for sodium electricity according to claim 2, wherein in the step 7, the stirring speed is reduced to 300-500rpm, and the precursor slurry is obtained after constant temperature maintenance for 2 hours.
10. The method for preparing a quaternary precursor for sodium electricity according to claim 2, wherein in the step 9, the precursor is prepared into a finished product and Na 2 CO 3 Placing the materials into a mixer according to the proportion of 1:1-1:1.07 for uniform mixing; placing the mixed materials into an atmosphere furnace, and preserving the temperature for 12-24 hours at 850-1000 ℃.
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