CN117466343A - Monocrystal nickel cobalt lithium manganate precursor and preparation method thereof - Google Patents
Monocrystal nickel cobalt lithium manganate precursor and preparation method thereof Download PDFInfo
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- CN117466343A CN117466343A CN202311742541.7A CN202311742541A CN117466343A CN 117466343 A CN117466343 A CN 117466343A CN 202311742541 A CN202311742541 A CN 202311742541A CN 117466343 A CN117466343 A CN 117466343A
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- 239000002243 precursor Substances 0.000 title claims abstract description 29
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 siloxane structure Chemical group 0.000 claims abstract description 25
- 239000003607 modifier Substances 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 16
- 150000001768 cations Chemical class 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 92
- 239000000178 monomer Substances 0.000 claims description 41
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- 229920001296 polysiloxane Polymers 0.000 claims description 22
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 16
- 230000003014 reinforcing effect Effects 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003623 enhancer Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims 4
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 4
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 2
- 159000000002 lithium salts Chemical class 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 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
-
- 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 discloses a monocrystal nickel cobalt lithium manganate precursor and a preparation method thereof, wherein a metal cation mixed solution is uniformly mixed with a sodium hydroxide solution, ammonia water is added to adjust the pH value, a modifier and DMF are added to react, deionized water is added to stand and filter the mixture to remove filtrate, a substrate is dried to obtain the monocrystal nickel cobalt lithium manganate precursor, diacetyl groups on a reinforcing agent, acetamido groups can be complexed with metal cations, a cage-shaped siloxane structure and an organosilicon molecular grid-shaped molecular chain on the reinforcing agent can play a role in preparation, after the precursor and lithium salt are compounded and sintered into a positive electrode material, the modifier is carbonized at a high temperature, the positive electrode material can be well prepared, electrode structure collapse in the circulation process is effectively prevented, the rapid decrease of the battery capacity is prevented, and the service life of the battery is further prolonged.
Description
Technical Field
The invention relates to the technical field of preparation of new energy materials, in particular to a monocrystal nickel cobalt lithium manganate precursor and a preparation method thereof.
Background
Lithium ion batteries are a novel green energy source and have long been a focus of attention in all communities. Along with further development of scientific technology, lithium ion batteries are gradually applied to the fields of high-capacity batteries such as power, energy storage and the like. Recently, from the aspects of safety and battery cost, it is widely considered internationally that lithium iron phosphate is the best positive electrode material of a novel high-energy power battery, and is the lithium ion battery positive electrode material most hopefully applied to a high-power battery; however, the material has small tap density, poor low-temperature performance, and the volume of equal capacity is obviously larger than that of other batteries, and the field of miniature batteries is not advantageous, while the nickel cobalt lithium manganate integrates the advantages of lithium nickelate and lithium cobaltate, is easy to synthesize and low in price, can be applied to miniature batteries and power batteries, has limited market share, and has obvious development potential. The monocrystal nickel cobalt lithium manganate precursor is used as the positive important component of lithium battery, and has stable structure, and becomes the key of the service life of the battery,
disclosure of Invention
The invention aims to provide a monocrystal nickel cobalt lithium manganate precursor and a preparation method thereof, which solve the problem that the positive electrode material prepared from the monocrystal nickel cobalt lithium manganate precursor in the current stage is easy to collapse.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the monocrystal nickel cobalt lithium manganate precursor specifically comprises the following steps:
step A1: taking nickel nitrate hexahydrate, cobalt nitrate hexahydrate and manganese nitrate solution as raw materials, and dissolving the raw materials in deionized water according to the mass ratio of positive ions of nickel to cobalt to manganese=1:1:1 to prepare a metal positive ion mixed solution;
step A2: uniformly mixing the metal cation mixed solution and a sodium hydroxide solution, adding ammonia water to adjust the pH value to be 10.5-11.5, adding a reinforcing agent and DMF at the rotating speed of 200-300r/min and the temperature of 70-80 ℃ for reacting for 20-24 hours, adding deionized water, standing and filtering to remove filtrate, and drying a substrate at the temperature of 140-150 ℃ for 20-25 hours to obtain the monocrystal nickel cobalt lithium manganate precursor.
Further, the volume ratio of the metal cation mixed solution to the sodium hydroxide solution in the step A2 is 1:1, and the concentration of the sodium hydroxide solution is 2.2mol/L.
Further, the reinforcing agent is prepared by the following steps:
step B1: mixing diphenyl dichlorosilane and deionized water, stirring for 10-15min at the rotation speed of 200-300r/min and the temperature of 60-70 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 4-6h, regulating pH to be neutral to obtain hydrogen-terminated polysiloxane, uniformly mixing pentaerythritol, acrylic acid, p-toluenesulfonic acid and DMF, and reacting for 6-8h at the rotation speed of 150-200r/min and the temperature of 110-120 ℃ to obtain a reinforced monomer;
step B2: uniformly mixing hydrogen-terminated polysiloxane, a reinforcing monomer and DMF (dimethyl formamide), stirring and adding chloroplatinic acid at the rotating speed of 150-200r/min and the temperature of 50-60 ℃, reacting for 10-15h, adding KH570, continuously reacting for 8-10h to obtain a modified monomer, uniformly mixing the modified monomer, KH560, a tetramethyl ammonium hydroxide aqueous solution and DMF, stirring at the rotating speed of 200-300r/min and the temperature of 25-30 ℃ for 20-24h, heating to 60-70 ℃, reacting for 4-6h, aging for 7 days, and filtering to remove filtrate to obtain a modifier;
step B3: dissolving a modifier in DMF, adding polyvinyl alcohol and sodium hydroxide, reacting for 6-8h at the rotation speed of 150-200r/min and the temperature of 25-30 ℃, adjusting the pH value to 1-2, heating to 85-90 ℃, adding methyl acetoacetate, reacting for 4-6h, distilling to remove DMF, adding deionized water, filtering to remove filtrate, and drying a substrate to obtain the reinforcing agent.
Further, the dosage ratio of the diphenyldichlorosilane, the deionized water and the 1, 3-tetramethyl disiloxane in the step B1 is 1mmol to 20mL to 2mmol, the dosage of the concentrated sulfuric acid is 1-3% of the sum of the mass of the diphenyldichlorosilane and the mass of the 1, 3-tetramethyl disiloxane, the molar ratio of the pentaerythritol to the acrylic acid is 1:4, and the dosage of the p-toluenesulfonic acid is 3% of the sum of the mass of the pentaerythritol and the acrylic acid.
Further, the molar ratio of the hydrogen-terminated polysiloxane to the reinforcing monomer to KH570 in the step B2 is 4:1:4, the concentration of chloroplatinic acid in the mixed system of the hydrogen-terminated polysiloxane, the reinforcing monomer, DMF, chloroplatinic acid and KH570 is 15-20ppm, the dosage ratio of the modifying monomer to KH560 to the aqueous solution of tetramethylammonium hydroxide is 10mmol to 100mmol to 40mL, and the mass fraction of the aqueous solution of tetramethylammonium hydroxide is 25%.
Further, the dosage ratio of the modifier to the polyvinyl alcohol to the methyl acetoacetate in the step B3 is 0.2g to 5g to 12.5mL, and the molecular weight of the polyvinyl alcohol is 16000-20000.
The invention has the beneficial effects that: the monocrystal nickel cobalt lithium manganate precursor is prepared through mixing metal cation mixture with sodium hydroxide solution, adding ammonia water to regulate pH to alkali, adding modifier and DMF to react, adding deionized water, standing, filtering to eliminate filtrate, drying substrate to obtain the monocrystal nickel cobalt lithium manganate precursor, hydrolyzing diphenyl dichlorosilane as material with modifier, polymerizing with 1, 3-tetramethyl disiloxane to form hydrogen terminated polysiloxane, acrylating pentaerythritol to obtain reinforced monomer, reacting Si-H bond on the hydrogen terminated polysiloxane with double bond on the reinforced monomer under the action of chloroplatinic acid, reacting with residual Si-H bond of KH570 to obtain modified monomer, hydrolyzing and polymerizing the modified monomer with KH560, the end of the modified monomer is provided with a cage structure and contains epoxy groups, the modifier is prepared, the modifier is reacted with polyvinyl alcohol, so that the epoxy groups on the modifier react with partial hydroxyl groups on the polyvinyl alcohol, and then are subjected to transesterification with methyl acetoacetate, and diacetyl groups are introduced to prepare the enhancer, the diacetyl groups on the enhancer can be complexed with metal cations, meanwhile, the cage siloxane structure and the organic silicon molecular grid molecular chains on the enhancer can play a role in preparing, after the precursor and the lithium salt are compounded and sintered into the positive electrode material, the modifier is carbonized at a high temperature, so that the positive electrode material can be prepared well, electrode structure collapse in the circulation process is effectively prevented, the battery capacity is prevented from being reduced rapidly, and the service life of the battery is prolonged.
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.
Example 1
The preparation method of the monocrystal nickel cobalt lithium manganate precursor specifically comprises the following steps:
step A1: taking nickel nitrate hexahydrate, cobalt nitrate hexahydrate and manganese nitrate solution as raw materials, and dissolving the raw materials in deionized water according to the mass ratio of positive ions of nickel to cobalt to manganese=1:1:1 to prepare a metal positive ion mixed solution;
step A2: uniformly mixing the metal cation mixed solution with a sodium hydroxide solution, adding ammonia water to adjust the pH value to 10.5, adding a reinforcing agent and DMF (dimethyl formamide) under the conditions of the rotating speed of 200r/min and the temperature of 70 ℃, reacting for 20 hours, adding deionized water, standing and filtering to remove filtrate, and drying a substrate for 20 hours under the conditions of the temperature of 140 ℃ to obtain the monocrystal nickel cobalt lithium manganate precursor.
The volume ratio of the metal cation mixed solution to the sodium hydroxide solution in the step A2 is 1:1, and the concentration of the sodium hydroxide solution is 2.2mol/L.
The reinforcing agent is prepared by the following steps:
step B1: mixing diphenyl dichlorosilane and deionized water, stirring for 10min at the rotation speed of 200r/min and the temperature of 60 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 4h, adjusting pH to be neutral to obtain hydrogen-terminated polysiloxane, uniformly mixing pentaerythritol, acrylic acid, p-toluenesulfonic acid and DMF, and reacting for 6h at the rotation speed of 150r/min and the temperature of 110 ℃ to obtain a reinforced monomer;
step B2: uniformly mixing hydrogen-terminated polysiloxane, a reinforcing monomer and DMF (dimethyl formamide), stirring and adding chloroplatinic acid at the rotating speed of 150r/min and the temperature of 50 ℃, reacting for 10 hours, adding KH570, continuously reacting for 8 hours to obtain a modified monomer, uniformly mixing the modified monomer, KH560, a tetramethyl ammonium hydroxide aqueous solution and DMF, stirring at the rotating speed of 200r/min and the temperature of 25 ℃ for 20 hours, heating to 60 ℃, reacting for 4 hours, aging for 7 days, filtering to remove filtrate, and obtaining a modifier;
step B3: dissolving a modifier in DMF, adding polyvinyl alcohol and sodium hydroxide, reacting for 6 hours at the rotation speed of 150r/min and the temperature of 25 ℃, adjusting the pH value to 1, heating to 85 ℃, adding methyl acetoacetate, reacting for 4 hours, distilling to remove DMF, adding deionized water, filtering to remove filtrate, and drying a substrate to obtain the reinforcing agent.
The dosage ratio of the diphenyldichlorosilane to the deionized water to the 1, 3-tetramethyl disiloxane in the step B1 is 1mmol to 20mL to 2mmol, the dosage of the concentrated sulfuric acid is 1% of the sum of the mass of the diphenyldichlorosilane and the mass of the 1, 3-tetramethyl disiloxane, the molar ratio of the pentaerythritol to the acrylic acid is 1:4, and the dosage of the p-toluenesulfonic acid is 3% of the sum of the mass of the pentaerythritol and the acrylic acid.
The molar ratio of the hydrogen-terminated polysiloxane to the reinforcing monomer to KH570 in the step B2 is 4:1:4, the concentration of chloroplatinic acid in the mixed system of the hydrogen-terminated polysiloxane, the reinforcing monomer, DMF, chloroplatinic acid and KH570 is 15ppm, the dosage ratio of the modified monomer to KH560 to the aqueous solution of tetramethylammonium hydroxide is 10mmol to 100mmol to 40mL, and the mass fraction of the aqueous solution of tetramethylammonium hydroxide is 25%.
The dosage ratio of the modifier to the polyvinyl alcohol to the methyl acetoacetate in the step B3 is 0.2g to 5g to 12.5mL, and the molecular weight of the polyvinyl alcohol is 16000.
Example 2
The preparation method of the monocrystal nickel cobalt lithium manganate precursor specifically comprises the following steps:
step A1: taking nickel nitrate hexahydrate, cobalt nitrate hexahydrate and manganese nitrate solution as raw materials, and dissolving the raw materials in deionized water according to the mass ratio of positive ions of nickel to cobalt to manganese=1:1:1 to prepare a metal positive ion mixed solution;
step A2: uniformly mixing the metal cation mixed solution with a sodium hydroxide solution, adding ammonia water to adjust the pH value to 11, adding a reinforcing agent and DMF (dimethyl formamide) under the conditions of the rotating speed of 200r/min and the temperature of 75 ℃ for reacting for 22 hours, adding deionized water, standing and filtering to remove filtrate, and drying a substrate for 23 hours under the conditions of the temperature of 145 ℃ to obtain the monocrystal nickel cobalt lithium manganate precursor.
The volume ratio of the metal cation mixed solution to the sodium hydroxide solution in the step A2 is 1:1, and the concentration of the sodium hydroxide solution is 2.2mol/L.
The reinforcing agent is prepared by the following steps:
step B1: mixing diphenyl dichlorosilane and deionized water, stirring for 13min at the speed of 200r/min and the temperature of 65 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 5h, adjusting pH to be neutral to obtain hydrogen-terminated polysiloxane, uniformly mixing pentaerythritol, acrylic acid, p-toluenesulfonic acid and DMF, and reacting for 7h at the speed of 150r/min and the temperature of 115 ℃ to obtain a reinforced monomer;
step B2: uniformly mixing hydrogen-terminated polysiloxane, a reinforcing monomer and DMF (dimethyl formamide), stirring and adding chloroplatinic acid at the rotating speed of 150r/min and the temperature of 55 ℃, reacting for 10-15h, adding KH570, continuously reacting for 9h to obtain a modified monomer, uniformly mixing the modified monomer, KH560, a tetramethyl ammonium hydroxide aqueous solution and DMF, stirring at the rotating speed of 200r/min and the temperature of 28 ℃ for 22h, heating to 65 ℃, reacting for 5h, aging for 7 days, filtering to remove filtrate, and obtaining the modifier;
step B3: dissolving a modifier in DMF, adding polyvinyl alcohol and sodium hydroxide, reacting for 7 hours at the rotation speed of 150r/min and the temperature of 28 ℃, adjusting the pH value to 2, heating to 88 ℃, adding methyl acetoacetate, reacting for 5 hours, distilling to remove DMF, adding deionized water, filtering to remove filtrate, and drying a substrate to obtain the reinforcing agent.
The dosage ratio of the diphenyldichlorosilane to the deionized water to the 1, 3-tetramethyldisiloxane in the step B1 is 1mmol to 20mL to 2mmol, the dosage of the concentrated sulfuric acid is 2% of the sum of the mass of the diphenyldichlorosilane and the mass of the 1, 3-tetramethyldisiloxane, the molar ratio of the pentaerythritol to the acrylic acid is 1:4, and the dosage of the p-toluenesulfonic acid is 3% of the sum of the mass of the pentaerythritol and the acrylic acid.
The molar ratio of the hydrogen-terminated polysiloxane to the reinforcing monomer to KH570 in the step B2 is 4:1:4, the concentration of chloroplatinic acid in the mixed system of the hydrogen-terminated polysiloxane, the reinforcing monomer, DMF, chloroplatinic acid and KH570 is 18ppm, the dosage ratio of the modified monomer to KH560 to the aqueous solution of tetramethylammonium hydroxide is 10mmol to 100mmol to 40mL, and the mass fraction of the aqueous solution of tetramethylammonium hydroxide is 25%.
The dosage ratio of the modifier to the polyvinyl alcohol to the methyl acetoacetate in the step B3 is 0.2g to 5g to 12.5mL, and the molecular weight of the polyvinyl alcohol is 18000.
Example 3
The preparation method of the monocrystal nickel cobalt lithium manganate precursor specifically comprises the following steps:
step A1: taking nickel nitrate hexahydrate, cobalt nitrate hexahydrate and manganese nitrate solution as raw materials, and dissolving the raw materials in deionized water according to the mass ratio of positive ions of nickel to cobalt to manganese=1:1:1 to prepare a metal positive ion mixed solution;
step A2: uniformly mixing the metal cation mixed solution with a sodium hydroxide solution, adding ammonia water to adjust the pH value to 11.5, adding a reinforcing agent and DMF (dimethyl formamide) under the conditions of the rotating speed of 300r/min and the temperature of 80 ℃, reacting for 24 hours, adding deionized water, standing and filtering to remove filtrate, and drying a substrate for 25 hours under the conditions of the temperature of 150 ℃ to obtain the monocrystal nickel cobalt lithium manganate precursor.
The volume ratio of the metal cation mixed solution to the sodium hydroxide solution in the step A2 is 1:1, and the concentration of the sodium hydroxide solution is 2.2mol/L.
The reinforcing agent is prepared by the following steps:
step B1: mixing diphenyl dichlorosilane and deionized water, stirring for 15min at the rotation speed of 300r/min and the temperature of 70 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 6h, adjusting pH to be neutral to obtain hydrogen-terminated polysiloxane, uniformly mixing pentaerythritol, acrylic acid, p-toluenesulfonic acid and DMF, and reacting for 8h at the rotation speed of 200r/min and the temperature of 120 ℃ to obtain a reinforced monomer;
step B2: uniformly mixing hydrogen-terminated polysiloxane, a reinforcing monomer and DMF (dimethyl formamide), stirring and adding chloroplatinic acid at the rotating speed of 200r/min and the temperature of 60 ℃, reacting for 15 hours, adding KH570, continuously reacting for 10 hours to obtain a modified monomer, uniformly mixing the modified monomer, KH560, a tetramethyl ammonium hydroxide aqueous solution and DMF, stirring at the rotating speed of 300r/min and the temperature of 30 ℃ for 24 hours, heating to 70 ℃, reacting for 6 hours, aging for 7 days, filtering to remove filtrate, and obtaining the modifier;
step B3: dissolving a modifier in DMF, adding polyvinyl alcohol and sodium hydroxide, reacting for 8 hours at the rotation speed of 200r/min and the temperature of 30 ℃, adjusting the pH value to 2, heating to 90 ℃, adding methyl acetoacetate, reacting for 6 hours, distilling to remove DMF, adding deionized water, filtering to remove filtrate, and drying a substrate to obtain the reinforcing agent.
The dosage ratio of the diphenyldichlorosilane to the deionized water to the 1, 3-tetramethyl disiloxane in the step B1 is 1mmol to 20mL to 2mmol, the dosage of the concentrated sulfuric acid is 3% of the sum of the mass of the diphenyldichlorosilane and the mass of the 1, 3-tetramethyl disiloxane, the molar ratio of the pentaerythritol to the acrylic acid is 1:4, and the dosage of the p-toluenesulfonic acid is 3% of the sum of the mass of the pentaerythritol and the acrylic acid.
The molar ratio of the hydrogen-terminated polysiloxane to the reinforcing monomer to KH570 in the step B2 is 4:1:4, the concentration of chloroplatinic acid in the mixed system of the hydrogen-terminated polysiloxane, the reinforcing monomer, DMF, chloroplatinic acid and KH570 is 20ppm, the dosage ratio of the modified monomer to KH560 to the aqueous solution of tetramethylammonium hydroxide is 10mmol to 100mmol to 40mL, and the mass fraction of the aqueous solution of tetramethylammonium hydroxide is 25%.
The dosage ratio of the modifier to the polyvinyl alcohol to the methyl acetoacetate in the step B3 is 0.2g to 5g to 12.5mL, and the molecular weight of the polyvinyl alcohol is 20000.
Comparative example 1
In this comparative example, no reinforcing agent was added as compared with example 1, and the rest of the procedure was the same.
Comparative example 2
This comparative example uses a modifier instead of a strengthening agent as compared to example 1, with the remainder of the procedure being the same.
Comparative example 3
This comparative example was used to add reinforcing monomer as compared to example 1, with the remainder of the procedure being the same.
The precursors prepared in examples 1-3 and comparative examples 1-3 were used as the positive electrode of the battery, acetylene black was used as the conductive agent, polytetrafluoroethylene emulsion was used as the adhesive, the mixture was mixed in a mass ratio of 86:11:8, and then the mixture was tabletted to prepare a positive electrode sheet, and metallic lithium was used as the negative electrode sheet of the battery, and the separator was a lithium battery separator manufactured by Chongqing Yuntian new york technology Co., ltd, liPF with a concentration of 1.2mol/L 6 And (2) preparing a simple battery from a solution of (EC) and DMC (DMC, wherein the volume ratio of the EC to DMC is 1:1), and carrying out constant-current charge and discharge test at the room temperature with the multiplying power of 0.2C (32 mA/g) within the voltage range of 2.8-4.3V, and observing whether structural collapse occurs in the positive electrode material for 30 times, 50 times and 100 times in a circulating way, wherein the detection results are shown in the table below.
From the above table, the positive electrode material has the effect of protecting the positive electrode material from collapse.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (7)
1. A preparation method of a monocrystal nickel cobalt lithium manganate precursor is characterized by comprising the following steps of: the method specifically comprises the following steps:
step A1: taking nickel nitrate hexahydrate, cobalt nitrate hexahydrate and manganese nitrate solution as raw materials, and dissolving the raw materials in deionized water according to the mass ratio of positive ions of nickel to cobalt to manganese=1:1:1 to prepare a metal positive ion mixed solution;
step A2: and uniformly mixing the metal cation mixed solution with a sodium hydroxide solution, adding ammonia water to adjust the pH value to be alkaline, adding an enhancer and DMF (dimethyl formamide), reacting, adding deionized water, standing, filtering to remove filtrate, and drying a substrate to obtain the monocrystal nickel cobalt lithium manganate precursor.
2. The method for preparing a monocrystal nickel cobalt lithium manganate precursor according to claim 1, which is characterized in that: the volume ratio of the metal cation mixed solution to the sodium hydroxide solution in the step A2 is 1:1.
3. The method for preparing a monocrystal nickel cobalt lithium manganate precursor according to claim 1, which is characterized in that: the reinforcing agent is prepared by the following steps:
step B1: after mixing and stirring diphenyl dichlorosilane and deionized water, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting, adjusting pH to be neutral to obtain hydrogen-terminated polysiloxane, and mixing pentaerythritol, acrylic acid, p-toluenesulfonic acid and DMF for reacting to obtain a reinforced monomer;
step B2: mixing and stirring hydrogen-terminated polysiloxane, a reinforcing monomer and DMF, adding chloroplatinic acid, reacting, adding KH570, continuing to react to obtain a modified monomer, mixing and stirring the modified monomer, KH560, an aqueous solution of tetramethylammonium hydroxide and DMF, heating to continue the reaction, aging, filtering to remove filtrate, and obtaining the modifier;
step B3: dissolving the modifier in DMF, adding polyvinyl alcohol and sodium hydroxide for reaction, adjusting pH to be acidic, heating, adding methyl acetoacetate for reaction, distilling to remove DMF, adding deionized water for filtration to remove filtrate, and drying a substrate to obtain the enhancer.
4. A method for preparing a single crystal lithium nickel cobalt manganate precursor according to claim 3, wherein: the dosage ratio of the diphenyldichlorosilane to the deionized water to the 1, 3-tetramethyl disiloxane in the step B1 is 1mmol to 20mL to 2mmol, the dosage of the concentrated sulfuric acid is 1-3% of the sum of the mass of the diphenyldichlorosilane and the mass of the 1, 3-tetramethyl disiloxane, the molar ratio of the pentaerythritol to the acrylic acid is 1:4, and the dosage of the p-toluenesulfonic acid is 3% of the sum of the mass of the pentaerythritol and the mass of the acrylic acid.
5. A method for preparing a single crystal lithium nickel cobalt manganate precursor according to claim 3, wherein: the molar ratio of the hydrogen-terminated polysiloxane to the reinforcing monomer to the KH570 in the step B2 is 4:1:4, the concentration of chloroplatinic acid in the mixed system of the hydrogen-terminated polysiloxane, the reinforcing monomer, DMF, chloroplatinic acid and KH570 is 15-20ppm, and the dosage ratio of the modifying monomer to the aqueous solution of KH560 to the aqueous solution of tetramethylammonium hydroxide is 10mmol to 100mmol to 40mL.
6. A method for preparing a single crystal lithium nickel cobalt manganate precursor according to claim 3, wherein: the dosage ratio of the modifier to the polyvinyl alcohol to the methyl acetoacetate in the step B3 is 0.2g to 5g to 12.5mL, and the molecular weight of the polyvinyl alcohol is 16000-20000.
7. A single crystal nickel cobalt lithium manganate precursor characterized by: the preparation method according to any one of claims 1-6.
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| JP2010097816A (en) * | 2008-10-16 | 2010-04-30 | Toyo Ink Mfg Co Ltd | Positive mix paste for lithium secondary battery |
| CN102709544A (en) * | 2012-06-06 | 2012-10-03 | 中南大学 | Nickel cobalt lithium manganate composite cathode material and preparation method of nickel cobalt lithium manganate composite cathode material |
| CN112794376A (en) * | 2021-01-20 | 2021-05-14 | 湖南德景源科技有限公司 | Preparation method of nickel-cobalt-manganese ternary material precursor |
| CN117117328A (en) * | 2023-10-23 | 2023-11-24 | 深圳华驰新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
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| JP2010097816A (en) * | 2008-10-16 | 2010-04-30 | Toyo Ink Mfg Co Ltd | Positive mix paste for lithium secondary battery |
| CN102709544A (en) * | 2012-06-06 | 2012-10-03 | 中南大学 | Nickel cobalt lithium manganate composite cathode material and preparation method of nickel cobalt lithium manganate composite cathode material |
| CN112794376A (en) * | 2021-01-20 | 2021-05-14 | 湖南德景源科技有限公司 | Preparation method of nickel-cobalt-manganese ternary material precursor |
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