CN107644984A - A kind of NiTi manganese base lithium ion cell positive material and preparation method thereof - Google Patents

A kind of NiTi manganese base lithium ion cell positive material and preparation method thereof Download PDF

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CN107644984A
CN107644984A CN201710695203.0A CN201710695203A CN107644984A CN 107644984 A CN107644984 A CN 107644984A CN 201710695203 A CN201710695203 A CN 201710695203A CN 107644984 A CN107644984 A CN 107644984A
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niti
manganese
lithium ion
mixed solution
ion cell
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朱伟
赵宇翔
张小洪
赵朔
李龙
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Chongqing University
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Chongqing University
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a kind of NiTi manganese base lithium ion cell positive material and preparation method thereof；The chemical general formula of the positive electrode is LiNi1‑x‑y‑zTixMnyMzO2, wherein 0.025≤x ﹤ 0.2,0≤y ﹤ 0.4,0≤z ﹤ 0.05, the mol ratio of Ni components is the one or several kinds in 0.6 0.9, M Co, Cr, Nd, Fe, Cu.The present invention uses co-electrodeposition method, passes through following steps：1) by TiO2Or H2TiO3It is distributed in reaction bottom liquid；Or the complex of the soluble metallic salt of titanium, titanium is hydrolyzed in the liquid of bottom；2) aqueous solution of soluble metallic salt and sodium hydroxide solution, enveloping agent solution are added to parallel in reaction bottom liquid, are heating and NiTi manganese presoma is synthesized under the conditions of protective gas；3) presoma and lithium source mixing are weighed, then preheated processing, is cooled down, is crushed, screening obtains NiTi manganese lithium ion battery material.The product of the present invention has the advantages that height ratio capacity, low cost, processing and cycle performance are excellent.

Description

A kind of NiTi manganese base lithium ion cell positive material and preparation method thereof
Technical field
The present invention relates to lithium ion battery, specifically a kind of NiTi manganese base lithium ion cell positive material and its preparation side Method.
Background technology
Lithium ion battery (LIB) has extended cycle life, advantages of environment protection, is widely used to because energy density is high The power supply of the various equipment such as mobile electron, electric automobile (EV).Particularly core of the lithium ion battery as new-energy automobile One of part, just receive more and more attention.And anode material for lithium-ion batteries as the critical material in lithium ion battery it One, it is larger to account for the proportion of whole battery cost, is an important factor for influenceing lithium ion battery cost.
The ternary material of main flow such as LiNi in the market1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、 LiNi0.6Co0.2Mn0.2O2Deng all containing substantial amounts of cobalt.Because cobalt element abundance is low, resource is less, price is higher, turns into influence One of an important factor for lithium ion battery cost, leverage the large-scale application of lithium ion battery.
The positive pole cost of lithium ion battery is reduced, high from elemental abundance, price is low, while and can substantially improves material and followed The element of ring stability, be advantageous to lithium ion battery and widely apply.
The content of the invention
Present invention aim to address problems of the prior art, disclose a kind of NiTi manganese base lithium ion anode Material and preparation method thereof；
To realize that the technical scheme that the object of the invention uses is a kind of such, NiTi manganese base lithium ion anode material Material, it is characterised in that：The chemical general formula of the positive electrode is LiNi1-x-y-zTixMnyMzO2；
Wherein：0.025≤x ﹤ 0.2,0≤y ﹤ 0.4,0≤z ﹤ 0.05；
The mol ratio of Ni components is 0.6~0.9,
M is the one or several kinds in Co, Cr, Nd, Fe, Cu.
A kind of preparation method of NiTi manganese base lithium ion cell positive material, it is characterised in that comprise the following steps：
1) codeposition reactions prepare NiTi manganese presoma
1.1) in kettle device is reacted, using deionized water as reaction bottom liquid, by TiO2Or H2TiO3Divide in bottom liquid is reacted Dissipate uniformly, obtain mixture A；
The deionized water and TiO2Or H2TiO3The amount of material than scope be the ︰ 1 of 5 ︰ 1~10；
1.2) Ni and Mn soluble metallic salt is added in water, mixed solution B is obtained after dissolving；
The soluble metallic salt includes sulfate, nitrate or chlorate；
The ratio between the amount sum of described Ni, Mn material and the amount of material of water are the ︰ 100 of 1 ︰ 50~1；
1.3) precipitating reagent and complexing agent are mixed, obtains mixed solution C；
The precipitating reagent is sodium hydroxide solution；
The concentration range of the sodium hydroxide solution is 0.5~7.5mol/L；
The complexing agent include ammoniacal liquor, ammonium hydrogen carbonate, ammonium carbonate, citric acid or disodium ethylene diamine tetraacetate in one kind or It is several；
The molar ratio range of the precipitating reagent and complexing agent is the ︰ 2 of 1 ︰ 0.5~1；
The ratio of Ni and Mn amount of substance sum and the amount of the material of sodium hydroxide in the precipitating reagent in the mixed solution B Example is 1 ︰ 2；
1.4) by the mixed solution C obtained in the mixed solution B and step 1.3) that are obtained in step 1.2) and step is dripped to 1.1) in the mixture A obtained, heating with conditions of protective gas, carrying out codeposition reactions, obtain precursor product；
The ratio of Ni in Ti, step 1.2) and Mn in the step 1.1) are according to formula LiNi1-x-y-zTixMnyMzO2 Calculate, wherein：0.025≤x ﹤ 0.2,0≤y ﹤ 0.4,0≤z ﹤ 0.05；The mol ratio of Ni components is 0.6~0.9；
The heating temperature range is 40~80 DEG C；
The protective gas includes Ar or N2In one kind；
The reaction time is 10~12h；PH scopes in the course of reaction are 10.5~12.5；
1.5) after the precursor product obtained in step 1.4) being filtered, cleaned, NiTi manganese presoma is obtained；
2) after the NiTi manganese presoma obtained in step 1.5) being dried, sieved, with lithium source and M stoichiometrically It is thoroughly mixed, obtained mixture is filled into alms bowl, is obtained after high temperature sintering, broken, sieving, ventilation are dry under oxygen atmosphere NiTi manganese base lithium ion cell positive material；
The M is the one or several kinds in Co, Cr, Nd, Fe, Cu；
The time range of the high temperature sintering is 10~30 hours；
The temperature range of the high temperature sintering is 600~1000 DEG C.
A kind of preparation method of NiTi manganese base lithium ion cell positive material, it is characterised in that comprise the following steps：
1) codeposition reactions prepare NiTi manganese presoma
1.1) deionized water is added in kettle device is reacted as reaction bottom liquid, by the soluble-salt of titanium in bottom liquid is reacted It is uniformly dispersed, obtains mixture A；
The proportion of the amount of the deionized water and Ti material is the ︰ 1 of 5 ︰ 1~10；
The soluble-salt of the titanium includes titanyl sulfate, titanium trichloride or metatitanic acid fourth fat；
1.2) Ni and Mn soluble metallic salt is added in water, mixed solution B is obtained after dissolving；
The soluble metallic salt includes sulfate, nitrate or chlorate；
The ratio between the amount sum of described Ni, Mn material and the amount of material of water are the ︰ 100 of 1 ︰ 50~1；
1.3) precipitating reagent and complexing agent are mixed, obtains mixed solution C；
The precipitating reagent is sodium hydroxide solution；
The concentration range of the sodium hydroxide solution is 0.5~7.5mol/L；
The complexing agent include ammoniacal liquor, ammonium hydrogen carbonate, ammonium carbonate, citric acid or disodium ethylene diamine tetraacetate in one kind or It is several；
The molar ratio range of the precipitating reagent and complexing agent is the ︰ 2 of 1 ︰ 0.5~1；
The ratio of Ni and Mn amount of substance sum and the amount of the material of sodium hydroxide in the precipitating reagent in the mixed solution B Example is 1 ︰ 2；
1.4) by the mixed solution C obtained in the mixed solution B and step 1.3) that are obtained in step 1.2) and step is dripped to 1.1) in the mixture A obtained, heating with conditions of protective gas, carrying out codeposition reactions, obtain precursor product；
The ratio of Ni in Ti, step 1.2) and Mn in the step 1.1) are according to formula LiNi1-x-y-zTixMnyMzO2 Calculate, wherein：0.025≤x ﹤ 0.2,0≤y ﹤ 0.4,0≤z ﹤ 0.05；The mol ratio of Ni components is 0.6~0.9；
The heating temperature range is 40~80 DEG C；
The protective gas includes Ar or N2In one kind；
The reaction time is 10~12h；PH scopes in the course of reaction are 10.5~12.5；
1.5) after the precursor product obtained in step 1.4) being filtered, cleaned, NiTi manganese presoma is obtained；
2) after the NiTi manganese presoma obtained in step 1.5) being dried, sieved, with lithium source and M stoichiometrically It is thoroughly mixed, obtained mixture is filled into alms bowl, is obtained after high temperature sintering, broken, sieving, ventilation are dry under oxygen atmosphere NiTi manganese base lithium ion cell positive material；
The M is the one or several kinds in Co, Cr, Nd, Fe, Cu；
The time range of the high temperature sintering is 10~30 hours；
The temperature range of the high temperature sintering is 600~1000 DEG C.
Further, the TiO in the step 1.1)2To be one or two kinds of in Detitanium-ore-type or rutile-type.
Further, in the step 2) in drying course, temperature range is 70~100 DEG C, and time range is 5~10h.
Further, the lithium source in the step 2) includes the one or more in lithium hydroxide, lithium carbonate or lithia.
The solution have the advantages that unquestionable, the present invention has advantages below：
For problems of the prior art, the present invention replaces cobalt element to improve the circulation of material using titanium elements Stability, improve the security of material with manganese element, prepared NiTi manganese base lithium ion battery material.The material has higher Specific discharge capacity, preferable cyclical stability and relatively low cost, the advantages that processing and cycle performance are excellent.
Brief description of the drawings
Fig. 1 be embodiment 1 prepare NiTi manganese base ion battery positive electrode in the range of 2.5-4.3V, under 0.5C multiplying powers Cycle-index and specific discharge capacity figure；
Fig. 2 is the NiTi manganese base ion battery positive electrode of the preparation of embodiment 1 under 0.5C multiplying powers in the range of 2.5-4.3V Single-revolution charging and discharging curve figure；
Fig. 3 is the XRD of NiTi manganese base ion battery positive electrode prepared by embodiment 1；
Fig. 4 is the grain size distribution of NiTi manganese base ion battery positive electrode prepared by embodiment 1.
Embodiment
With reference to embodiment, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention only It is limited to following embodiments.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and used With means, various replacements and change are made, all should be included within the scope of the present invention.
Embodiment 1：
A kind of preparation method of NiTi manganese base lithium ion cell positive material, specifically LiNi0.8Ti0.1Mn0.1O2, it is special Sign is, comprises the following steps：
1) codeposition reactions prepare NiTi manganese presoma
1.1) 100mL deionized waters are added in kettle device is reacted as reaction bottom liquid, by 0.7983 gram of TiO2Reacting It is uniformly dispersed in the liquid of bottom, obtains mixture A；
Mixing speed in the dispersion process is 500r/min；
1.2) 21.028 grams of NiSO are added in 200mL water4·6H2O, 1.6902 grams of MnSO4·H2O, mixed after dissolving Close solution；
1.3) 7.2 grams of NaOH and 15mL ammoniacal liquor are settled to 200mL, are configured to ammonia alkali solution；
1.4) lead in 55 DEG C of waters bath with thermostatic control under conditions of argon gas protection, the ammonia alkali solution and step that will be obtained in step 1.3) It is rapid 1.2) in obtained mixed solution, and drip to mixture A institutes in a reservoir；It is 10.5~12.5 to control pH scopes；
Titration continues under 55 DEG C of waters bath with thermostatic control after terminating to stir ageing 10h under 500r/min rotating speed；Obtain forerunner Body product；
1.5) after the precursor product obtained in step 1.4) being filtered, cleaned, NiTi manganese presoma is obtained；
2) by gained presoma filter, washing, dry after and 4.6156 grams of LiOHH2O is mixed, and is situated between by ball milling of acetone Matter, the ball milling 10h under 300r/min, 10h is then sintered at 600~1000 DEG C in tube furnace oxygen atmosphere and obtains target production Thing.
By products therefrom, PVDF and Super-P according to 8:1:1 mass ratio, add 3.0 grams of 1-METHYLPYRROLIDONEs and divide After being dried at 100 DEG C, anode electrode piece of the area for 1 square centimeter is cut into sheet-punching machine coated on aluminium foil for powder.
Using lithium piece as negative pole, 1mol/L LiPF6/ EC+DMC makees electrolyte, using Cegard-2000 barrier films, in argon Button cell is assembled into gas glove box.
By button cell in new prestige battery detecting instrument system, with 0.5C charge-discharge tests in the range of 2.5~4.3V.Put Electric specific capacity reaches 162mAh/g.
As shown in figure 1, as embodiment 1 prepare NiTi manganese base ion battery positive electrode in the range of 2.5-4.3V, Cycle-index and specific discharge capacity figure under 0.5C multiplying powers；It can be seen that the sample highest being prepared in the present embodiment Specific discharge capacity reaches 172mAh/g, and capability retention is 82% after 200 circulations.Thus, the sample being prepared in the present embodiment Product show good cyclical stability；
As shown in Fig. 2 the NiTi manganese base ion battery positive electrode that as prepared by embodiment 1 is in the range of 2.5-4.3V Single-revolution charging and discharging curve figure under 0.5C multiplying powers；It can be seen that the material being prepared in the present embodiment follows at second The charging and discharging curve of ring, has reached 172mAh/g, shows that this material has higher charging and discharging capacity；
As shown in figure 3, as embodiment 1 prepare NiTi manganese base ion battery positive electrode XRD；Can be with from figure Find out, each diffraction maximum is all present and each peak is sharp, and free from admixture peak is present；
As shown in figure 4, as embodiment 1 prepare NiTi manganese base ion battery positive electrode grain size distribution；From figure In it can be seen that prepared material particle size in 10um or so, shows that the material has preferable processing characteristics.
Embodiment 2：
A kind of preparation method of NiTi manganese base lithium ion cell positive material, specifically LiNi0.6Ti0.1Mn0.3O2, it is special Sign is, comprises the following steps：
1) codeposition reactions prepare NiTi manganese presoma
1.1) 100mL deionized waters are added in kettle device is reacted as reaction bottom liquid, by 0.7983 gram of TiO2Reacting It is uniformly dispersed in the liquid of bottom, obtains mixture A；
Mixing speed in the dispersion process is 500r/min；
1.2) 17.4486 grams of Ni (NO are added in 200mL water3)2·6H2O, 7.5327 grams of Mn (NO3)2·4H2O, dissolving After obtain mixed solution；
1.3) 7.2 grams of NaOH and 15mL ammoniacal liquor are settled to 200mL, are configured to ammonia alkali solution；
1.4) lead in 55 DEG C of waters bath with thermostatic control under conditions of argon gas protection, the ammonia alkali solution and step that will be obtained in step 1.3) It is rapid 1.2) in obtained mixed solution, and drip to mixture A institutes in a reservoir；It is 10.5~12.5 to control pH scopes；
Titration continues under 55 DEG C of waters bath with thermostatic control after terminating to stir ageing 10h under 500r/min rotating speed；Obtain forerunner Body product；
1.5) after the precursor product obtained in step 1.4) being filtered, cleaned, NiTi manganese presoma is obtained；
2) by gained presoma filter, washing, dry after and 4.0639 grams of Li2CO3Mixing, using acetone as ball-milling medium, Ball milling 10h under 300r/min, 10h is then sintered at 600~1000 DEG C in tube furnace oxygen atmosphere and obtains target product.
By products therefrom, PVDF and Super-P according to 8:1:1 mass ratio, add 3.0 grams of 1-METHYLPYRROLIDONEs and divide After being dried at 100 DEG C, anode electrode piece of the area for 1 square centimeter is cut into sheet-punching machine coated on aluminium foil for powder.
Using lithium piece as negative pole, 1mol/L LiPF6/ EC+DMC makees electrolyte, using Cegard-2000 barrier films, in argon Button cell is assembled into gas glove box.
By button cell in new prestige battery detecting instrument system, with 0.5C charge-discharge tests in the range of 2.5~4.3V.Put Electric specific capacity reaches 149mAh/g.
Embodiment 3：
A kind of preparation method of NiTi manganese base lithium ion cell positive material, specifically LiNi0.7Ti0.15Mn0.15O2, it is special Sign is, comprises the following steps：
1) codeposition reactions prepare NiTi manganese presoma
1.1) 100mL deionized waters are added in kettle device is reacted as reaction bottom liquid, by 1.4675 grams of H2TiO3Reacting It is uniformly dispersed in the liquid of bottom, obtains mixture A；
Mixing speed in the dispersion process is 500r/min；
1.2) 9.0713 grams of NiCl are added in 200mL water2, 1.8876 grams of MnCl2, mixed solution is obtained after dissolving；
1.3) 6.8 grams of NaOH and 15mL ammoniacal liquor are settled to 200mL, are configured to ammonia alkali solution；
1.4) lead in 55 DEG C of waters bath with thermostatic control under conditions of argon gas protection, the ammonia alkali solution and step that will be obtained in step 1.3) It is rapid 1.2) in obtained mixed solution, and drip to mixture A institutes in a reservoir；It is 10.5~12.5 to control pH scopes；
Titration continues under 55 DEG C of waters bath with thermostatic control after terminating to stir ageing 10h under 500r/min rotating speed；Obtain forerunner Body product；
1.5) after the precursor product obtained in step 1.4) being filtered, cleaned, NiTi manganese presoma is obtained；
2) by gained presoma filter, washing, dry after and 1.6434 grams of Li2O is mixed, using acetone as ball-milling medium, Ball milling 10h under 300r/min, 10h is then sintered at 600~1000 DEG C in tube furnace oxygen atmosphere and obtains target product.
By products therefrom, PVDF and Super-P according to 8:1:1 mass ratio, add 3 grams of 1-METHYLPYRROLIDONEs and disperse After being dried at 100 DEG C, anode electrode piece of the area for 1 square centimeter is cut into sheet-punching machine coated on aluminium foil for agent.
Using lithium piece as negative pole, 1mol/L LiPF6/ EC+DMC makees electrolyte, using Cegard-2000 barrier films, in argon Button cell is assembled into gas glove box.
By button cell in new prestige battery detecting instrument system, with 0.5C charge-discharge tests in the range of 2.5~4.3V.Put Electric specific capacity reaches 152mAh/g.
Embodiment 4：
A kind of preparation method of NiTi manganese base lithium ion cell positive material, specifically LiNi0.75Ti0.1Mn0.15O2, it is special Sign is, comprises the following steps：
1) codeposition reactions prepare NiTi manganese presoma
1.1) 100mL deionized waters are added in kettle device is reacted as reaction bottom liquid, by 1.5995 grams of titanyl sulfates (TiOSO4·2H2O) it is uniformly dispersed in bottom liquid is reacted, obtains mixture A；
Mixing speed in the dispersion process is 500r/min；
1.2) 19.7138 grams of NiSO are added in 200mL water4·6H2O, 2.5353 grams of MnSO4·H2O, obtained after dissolving Mixed solution；
1.3) 7.2 grams of NaOH and 15mL ammoniacal liquor are settled to 200mL, are configured to ammonia alkali solution；
1.4) lead in 55 DEG C of waters bath with thermostatic control under conditions of argon gas protection, the ammonia alkali solution and step that will be obtained in step 1.3) It is rapid 1.2) in obtained mixed solution, and drip to mixture A institutes in a reservoir；It is 10.5~12.5 to control pH scopes；
Titration continues under 55 DEG C of waters bath with thermostatic control after terminating to stir ageing 10h under 500r/min rotating speed；Obtain forerunner Body product；
1.5) after the precursor product obtained in step 1.4) being filtered, cleaned, NiTi manganese presoma is obtained；
2) by gained presoma filter, washing, dry after and 4.6156 grams of LiOHH2O is mixed, and is situated between by ball milling of acetone Matter, the ball milling 10h under 300r/min, 10h is then sintered at 600~1000 DEG C in tube furnace oxygen atmosphere and obtains target production Thing.
By products therefrom, PVDF and Super-P according to 8:1:1 mass ratio, add 3 grams of 1-METHYLPYRROLIDONEs and disperse After being dried at 100 DEG C, anode electrode piece of the area for 1 square centimeter is cut into sheet-punching machine coated on aluminium foil for agent.
Using lithium piece as negative pole, 1mol/L LiPF6/ EC+DMC makees electrolyte, using Cegard-2000 barrier films, in argon Button cell is assembled into gas glove box.
By button cell in new prestige battery detecting instrument system, with 0.5C charge-discharge tests in the range of 2.5~4.3V.Put Electric specific capacity reaches 156mAh/g.
Embodiment 5：
A kind of preparation method of NiTi manganese base lithium ion cell positive material, specifically LiNi0.9Ti0.05Mn0.05O2, it is special Sign is, comprises the following steps：
1) codeposition reactions prepare NiTi manganese presoma
1.1) 100mL deionized waters are added in kettle device is reacted as reaction bottom liquid, by 0.3992 gram of TiO2Reacting It is uniformly dispersed in the liquid of bottom, obtains mixture A；
Mixing speed in the dispersion process is 500r/min；
1.2) 23.6565 grams of NiSO are added in 200mL water4·6H2O, 0.8451 gram of MnSO4·H2O, obtained after dissolving Mixed solution；
1.3) 7.6 grams of NaOH and 15mL ammoniacal liquor are settled to 200mL, are configured to ammonia alkali solution；
1.4) lead in 55 DEG C of waters bath with thermostatic control under conditions of argon gas protection, the ammonia alkali solution and step that will be obtained in step 1.3) It is rapid 1.2) in obtained mixed solution, and drip to mixture A institutes in a reservoir；It is 10.5~12.5 to control pH scopes；
Titration continues under 55 DEG C of waters bath with thermostatic control after terminating to stir ageing 10h under 500r/min rotating speed；Obtain forerunner Body product；
1.5) after the precursor product obtained in step 1.4) being filtered, cleaned, NiTi manganese presoma is obtained；
2) by gained presoma filter, washing, dry after and 4.6156 grams of LiOHH2O is mixed, and is situated between by ball milling of acetone Matter, the ball milling 10h under 300r/min, 10h is then sintered at 600~1000 DEG C in tube furnace oxygen atmosphere and obtains target production Thing.
By products therefrom, PVDF and Super-P according to 8:1:1 mass ratio, add 3 grams of 1-METHYLPYRROLIDONEs and disperse After being dried at 100 DEG C, anode electrode piece of the area for 1 square centimeter is cut into sheet-punching machine coated on aluminium foil for agent.
Using lithium piece as negative pole, 1mol/L LiPF6/ EC+DMC makees electrolyte, using Cegard-2000 barrier films, in argon Button cell is assembled into gas glove box.
By button cell in new prestige battery detecting instrument system, with 0.5C charge-discharge tests in the range of 2.5~4.3V.Put Electric specific capacity reaches 190mAh/g.
Embodiment 6：
A kind of preparation method of NiTi manganese base lithium ion cell positive material, specifically LiNi0.9Ti0.025Mn0.075O2, its It is characterised by, comprises the following steps：
1) codeposition reactions prepare NiTi manganese presoma
1.1) 100mL deionized waters are added in kettle device is reacted as reaction bottom liquid, by 0.1996 gram of TiO2Reacting It is uniformly dispersed in the liquid of bottom, obtains mixture A；
Mixing speed in the dispersion process is 500r/min；
1.2) 23.6565 grams of NiSO are added in 200mL water4·6H2O, 1.2676 grams of MnSO4·H2O, obtained after dissolving Mixed solution；
1.3) 7.8 grams of NaOH and 15mL ammoniacal liquor are settled to 200mL, are configured to ammonia alkali solution；
1.4) lead in 55 DEG C of waters bath with thermostatic control under conditions of argon gas protection, the ammonia alkali solution and step that will be obtained in step 1.3) It is rapid 1.2) in obtained mixed solution, and drip to mixture A institutes in a reservoir；It is 10.5~12.5 to control pH scopes；
Titration continues under 55 DEG C of waters bath with thermostatic control after terminating to stir ageing 10h under 500r/min rotating speed；Obtain forerunner Body product；
1.5) after the precursor product obtained in step 1.4) being filtered, cleaned, NiTi manganese presoma is obtained；
2) by gained presoma filter, washing, dry after and 4.6156 grams of LiOHH2O is mixed, and is situated between by ball milling of acetone Matter, the ball milling 10h under 300r/min, 10h is then sintered at 600~1000 DEG C in tube furnace oxygen atmosphere and obtains target production Thing.
By products therefrom, PVDF and Super-P according to 8:1:1 mass ratio, add 3 grams of 1-METHYLPYRROLIDONEs and disperse After being dried at 100 DEG C, anode electrode piece of the area for 1 square centimeter is cut into sheet-punching machine coated on aluminium foil for agent.
Using lithium piece as negative pole, 1mol/L LiPF6/ EC+DMC makees electrolyte, using Cegard-2000 barrier films, in argon Button cell is assembled into gas glove box.
By button cell in new prestige battery detecting instrument system, with 0.5C charge-discharge tests in the range of 2.5~4.3V.Put Electric specific capacity reaches 193mAh/g.
Embodiment 7：
A kind of preparation method of NiTi manganese base lithium ion cell positive material, specifically LiNi0.8Ti0.1Mn0.09Cr0.01O2, It is characterised in that it includes following steps：
1) codeposition reactions prepare NiTi manganese presoma
1.1) 100mL deionized waters are added in kettle device is reacted as reaction bottom liquid, by 0.7983 gram of TiO2Reacting It is uniformly dispersed in the liquid of bottom, obtains mixture A；
Mixing speed in the dispersion process is 500r/min；
1.2) 21.028 grams of NiSO are added in 200mL water4·6H2O, 1.5212 grams of MnSO4·H2O, mixed after dissolving Close solution；
1.3) 7.2 grams of NaOH and 15mL ammoniacal liquor are settled to 200mL, are configured to ammonia alkali solution；
1.4) lead in 55 DEG C of waters bath with thermostatic control under conditions of argon gas protection, the ammonia alkali solution and step that will be obtained in step 1.3) It is rapid 1.2) in obtained mixed solution, and drip to mixture A institutes in a reservoir；It is 10.5~12.5 to control pH scopes；
Titration continues under 55 DEG C of waters bath with thermostatic control after terminating to stir ageing 10h under 500r/min rotating speed；Obtain forerunner Body product；
1.5) after the precursor product obtained in step 1.4) being filtered, cleaned, NiTi manganese presoma is obtained；
2) by gained presoma filter, washing, dry after with 0.0759 gram of Cr2O3With 4.6156 grams of LiOHH2O is mixed, Using acetone as ball-milling medium, the ball milling 10h under 300r/min, then sintered in tube furnace oxygen atmosphere at 600~1000 DEG C 10h obtains target product.
By products therefrom, PVDF and Super-P according to 8:1:1 mass ratio, add 3 grams of 1-METHYLPYRROLIDONEs and disperse After being dried at 100 DEG C, anode electrode piece of the area for 1 square centimeter is cut into sheet-punching machine coated on aluminium foil for agent.
Using lithium piece as negative pole, 1mol/L LiPF6/ EC+DMC makees electrolyte, using Cegard-2000 barrier films, in argon Button cell is assembled into gas glove box.
By button cell in new prestige battery detecting instrument system, with 0.5C charge-discharge tests in the range of 2.5~4.3V.Put Electric specific capacity reaches 173mAh/g.

Claims (6)

  1. A kind of 1. NiTi manganese base lithium ion cell positive material, it is characterised in that：The chemical general formula of the positive electrode is LiNi1-x-y-zTixMnyMzO2；
    Wherein：0.025≤x ﹤ 0.2,0≤y ﹤ 0.4,0≤z ﹤ 0.05；
    The mol ratio of Ni components is 0.6~0.9,
    M is the one or several kinds in Co, Cr, Nd, Fe, Cu.
  2. 2. a kind of preparation method of NiTi manganese base lithium ion cell positive material, it is characterised in that comprise the following steps：
    1) codeposition reactions prepare NiTi manganese presoma
    1.1) in kettle device is reacted, using deionized water as reaction bottom liquid, by TiO2Or H2TiO3Disperse in bottom liquid is reacted equal It is even, obtain mixture A；
    The deionized water and TiO2Or H2TiO3The amount of material than scope be the ︰ 1 of 5 ︰ 1~10；
    1.2) Ni and Mn soluble metallic salt is added in water, mixed solution B is obtained after dissolving；
    The soluble metallic salt includes sulfate, nitrate or chlorate；
    The ratio between the amount sum of described Ni, Mn material and the amount of material of water are the ︰ 100 of 1 ︰ 50~1；
    1.3) precipitating reagent and complexing agent are mixed, obtains mixed solution C；
    The precipitating reagent is sodium hydroxide solution；
    The concentration range of the sodium hydroxide solution is 0.5~7.5mol/L；
    The complexing agent includes one kind or several in ammoniacal liquor, ammonium hydrogen carbonate, ammonium carbonate, citric acid or disodium ethylene diamine tetraacetate Kind；
    The molar ratio range of the precipitating reagent and complexing agent is the ︰ 2 of 1 ︰ 0.5~1；
    The ratio of the amount of the material of sodium hydroxide is in Ni and Mn amount of substance sum and the precipitating reagent in the mixed solution B 1 ︰ 2；
    1.4) by the mixed solution C obtained in the mixed solution B and step 1.3) that are obtained in step 1.2) and step 1.1) is dripped to In obtained mixture A, heating with conditions of protective gas, carrying out codeposition reactions, obtain precursor product；
    The ratio of Ni in Ti, step 1.2) and Mn in the step 1.1) are according to formula LiNi1-x-y-zTixMnyMzO2Calculate, Wherein：0.025≤x ﹤ 0.2,0≤y ﹤ 0.4,0≤z ﹤ 0.05；The mol ratio of Ni components is 0.6~0.9；
    The heating temperature range is 40~80 DEG C；
    The protective gas includes Ar or N2In one kind；
    The reaction time is 10~12h；PH scopes in the course of reaction are 10.5~12.5；
    1.5) after the precursor product obtained in step 1.4) being filtered, cleaned, NiTi manganese presoma is obtained；
    2) it is stoichiometrically abundant with lithium source and M after the NiTi manganese presoma obtained in step 1.5) being dried, sieved It is stirred, obtained mixture is filled into alms bowl, NiTi is obtained after high temperature sintering, broken, sieving, ventilation are dry under oxygen atmosphere Manganese base lithium ion cell positive material；
    The M is the one or several kinds in Co, Cr, Nd, Fe, Cu；
    The time range of the high temperature sintering is 10~30 hours；
    The temperature range of the high temperature sintering is 600~1000 DEG C.
  3. 3. a kind of preparation method of NiTi manganese base lithium ion cell positive material, it is characterised in that comprise the following steps：
    1) codeposition reactions prepare NiTi manganese presoma
    1.1) deionized water is added in kettle device is reacted as reaction bottom liquid, the soluble-salt of titanium is disperseed in bottom liquid is reacted Uniformly, mixture A is obtained；
    The proportion of the amount of the deionized water and Ti material is the ︰ 1 of 5 ︰ 1~10；
    The soluble-salt of the titanium includes titanyl sulfate, titanium trichloride or metatitanic acid fourth fat；
    1.2) Ni and Mn soluble metallic salt is added in water, mixed solution B is obtained after dissolving；
    The soluble metallic salt includes sulfate, nitrate or chlorate；
    The ratio between the amount sum of described Ni, Mn material and the amount of material of water are the ︰ 100 of 1 ︰ 50~1；
    1.3) precipitating reagent and complexing agent are mixed, obtains mixed solution C；
    The precipitating reagent is sodium hydroxide solution；
    The concentration range of the sodium hydroxide solution is 0.5~7.5mol/L；
    The complexing agent includes one kind or several in ammoniacal liquor, ammonium hydrogen carbonate, ammonium carbonate, citric acid or disodium ethylene diamine tetraacetate Kind；
    The molar ratio range of the precipitating reagent and complexing agent is the ︰ 2 of 1 ︰ 0.5~1；
    The ratio of the amount of the material of sodium hydroxide is in Ni and Mn amount of substance sum and the precipitating reagent in the mixed solution B 1 ︰ 2；
    1.4) by the mixed solution C obtained in the mixed solution B and step 1.3) that are obtained in step 1.2) and step 1.1) is dripped to In obtained mixture A, heating with conditions of protective gas, carrying out codeposition reactions, obtain precursor product；
    The ratio of Ni in Ti, step 1.2) and Mn in the step 1.1) are according to formula LiNi1-x-y-zTixMnyMzO2Calculate, Wherein：0.025≤x ﹤ 0.2,0≤y ﹤ 0.4,0≤z ﹤ 0.05；The mol ratio of Ni components is 0.6~0.9；
    The heating temperature range is 40~80 DEG C；
    The protective gas includes Ar or N2In one kind；
    The reaction time is 10~12h；PH scopes in the course of reaction are 10.5~12.5；
    1.5) after the precursor product obtained in step 1.4) being filtered, cleaned, NiTi manganese presoma is obtained；
    2) it is stoichiometrically abundant with lithium source and M after the NiTi manganese presoma obtained in step 1.5) being dried, sieved It is stirred, obtained mixture is filled into alms bowl, NiTi is obtained after high temperature sintering, broken, sieving, ventilation are dry under oxygen atmosphere Manganese base lithium ion cell positive material；
    The M is the one or several kinds in Co, Cr, Nd, Fe, Cu；
    The time range of the high temperature sintering is 10~30 hours；
    The temperature range of the high temperature sintering is 600~1000 DEG C.
  4. A kind of 4. preparation method of NiTi manganese base lithium ion cell positive material according to claim 2, it is characterised in that： TiO in the step 1.1)2To be one or two kinds of in Detitanium-ore-type or rutile-type.
  5. 5. a kind of preparation method of NiTi manganese base lithium ion cell positive material according to Claims 2 or 3, its feature exist In：In the step 2) in drying course, temperature range is 70~100 DEG C, and time range is 5~10h.
  6. 6. a kind of preparation method of NiTi manganese base lithium ion cell positive material according to Claims 2 or 3, its feature exist In：Lithium source in the step 2) includes the one or more in lithium hydroxide, lithium carbonate or lithia.
CN201710695203.0A 2017-08-15 2017-08-15 A kind of NiTi manganese base lithium ion cell positive material and preparation method thereof Pending CN107644984A (en)

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CN108807973A (en) * 2018-06-28 2018-11-13 重庆大学 A kind of nickelic titanium-based anode material for lithium-ion batteries and preparation method thereof
CN109301243A (en) * 2018-12-10 2019-02-01 北京理工大学 A kind of stratiform nickel cobalt titanium tertiary cathode material and preparation method thereof
CN112072092A (en) * 2020-09-17 2020-12-11 杭州肄康新材料有限公司 Electrode material, preparation method thereof and lithium battery adopting electrode material
CN114436346A (en) * 2022-02-15 2022-05-06 佛山科学技术学院 Preparation method for preparing high-nickel ternary single crystal material precursor by coprecipitation method
CN116143196A (en) * 2023-02-27 2023-05-23 荆门市格林美新材料有限公司 Sodium ion battery positive electrode material and preparation method and application thereof

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CN104966833A (en) * 2015-07-28 2015-10-07 宁德时代新能源科技有限公司 Positive electrode material and preparation method thereof as well as lithium ion battery containing positive electrode material
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CN104966833A (en) * 2015-07-28 2015-10-07 宁德时代新能源科技有限公司 Positive electrode material and preparation method thereof as well as lithium ion battery containing positive electrode material
CN106058172A (en) * 2016-06-13 2016-10-26 合肥国轩高科动力能源有限公司 Quaternary nickel cobalt magnesium titanium cathode material of lithium ion battery, and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807973A (en) * 2018-06-28 2018-11-13 重庆大学 A kind of nickelic titanium-based anode material for lithium-ion batteries and preparation method thereof
CN109301243A (en) * 2018-12-10 2019-02-01 北京理工大学 A kind of stratiform nickel cobalt titanium tertiary cathode material and preparation method thereof
CN112072092A (en) * 2020-09-17 2020-12-11 杭州肄康新材料有限公司 Electrode material, preparation method thereof and lithium battery adopting electrode material
CN114436346A (en) * 2022-02-15 2022-05-06 佛山科学技术学院 Preparation method for preparing high-nickel ternary single crystal material precursor by coprecipitation method
CN116143196A (en) * 2023-02-27 2023-05-23 荆门市格林美新材料有限公司 Sodium ion battery positive electrode material and preparation method and application thereof

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