CN109768274A - Cell positive material presoma, cell positive material, preparation method and application - Google Patents
Cell positive material presoma, cell positive material, preparation method and application Download PDFInfo
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- CN109768274A CN109768274A CN201910040362.6A CN201910040362A CN109768274A CN 109768274 A CN109768274 A CN 109768274A CN 201910040362 A CN201910040362 A CN 201910040362A CN 109768274 A CN109768274 A CN 109768274A
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Abstract
The invention discloses a kind of preparation methods of cell positive material presoma, comprising: dissolves Ni base nitrate, Co base nitrate, Mn base nitrate and Cd base nitrate in dehydrated alcohol, obtains mixed solution；The mixed solution is subjected to solvent thermal reaction, makes Ni, Co, Mn and Cd element co-precipitation, and post-process to obtained sediment, obtains the cell positive material presoma of Ni-Co-Mn-Cd base.The present invention utilizes Ni, Co, Mn, the K of tetra- kinds of elements of CdspFour kinds of elements under co-precipitation, are obtained the cell positive material presoma of Ni-Co-Mn-Cd base during solvent-thermal process using solvent-thermal method, then mix the ternary cell positive material of Cd by the synthesis of high temperature solid-state roasting method by this close characteristic.Cd is capable of the structure of stabilizing material after doping, improves the electronic conductivity of material as a kind of inactive elemental with satisfactory electrical conductivity.
Description
Technical field
The present invention relates to a kind of cell positive material, in particular to a kind of cell positive material presoma, anode material
Material, preparation method and application.
Background technique
The nickelic positive electrode of stratiform is considered as most potential lithium ion due to its high capacity and low cost
One of cell positive material, however due to its undesirable cycle performance, storge quality, low coulombic efficiency is unstable with heat
Property limit it commercialization utilize.The main reason for causing this phenomenon is:
(1) due to Ni2+(0.069nm) and Li+The radius of (0.076nm) is identical, and Li occurs in the layered structure+/Ni2+'s
Mixing；
(2) edge response generation Li occurs for electrode and electrolyte interface2CO3Or the by-products such as LiOH, these disadvantages are to its electricity
Chemical property has a great impact.
In consideration of it, people often through modified mode disinthibite these influence chemical properties factor.Ion doping
It is considered as overcoming one of these difficult most efficient methods, is considered as a kind of simple raising nickelic positive electrode of stratiform
The method of structure and thermal stability, at present it has been reported that Doped ions mainly have Al3+, Mg2+, Ti4+, Mo6+, Nd3+And Na+Deng.
Although the mode of ion doping makes great progress on rock-steady structure and raising chemical property at present, these doping
The method of modifying overwhelming majority is to carry out element doping to material in the mixed lithium high-temperature roasting stage after driving body before the synthesis, few
The precursor synthesis stage is reported in the doping vario-property of material progress original position.
Compared to doping vario-property in situ, the doping vario-property of ex situ is difficult for doped chemical to be doped in body of material
The position of transition metal is occupied, while the doping way of ex situ is but also modifying process is more complicated.
Summary of the invention
The main purpose of the present invention is to provide a kind of cell positive material presomas, cell positive material, its preparation side
Method and application, to overcome deficiency in the prior art.
For achieving the above object, present invention employs following technical solutions:
A kind of preparation method of cell positive material presoma, comprising:
Ni base nitrate, Co base nitrate, Mn base nitrate and Cd base nitrate are dissolved in dehydrated alcohol, mixed
Close solution；
The mixed solution is subjected to solvent thermal reaction, makes Ni, Co, Mn and Cd element co-precipitation, and precipitate to obtaining
Object is post-processed, and the cell positive material presoma of Ni-Co-Mn-Cd base is obtained.
The embodiment of the invention also provides the cell positive material presomas being prepared by preceding method.
The embodiment of the invention also provides a kind of preparation methods of cell positive material, comprising:
The cell positive material presoma is mixed with lithium salts, preroast and roasting is successively carried out later, obtains Cd
The cell positive material of doping.
The embodiment of the invention also provides the cell positive materials being prepared by preceding method.
The embodiment of the invention also provides the cell positive material presomas or the cell positive material in system
Application in standby lithium ion battery.
Compared with the prior art, beneficial effects of the present invention are included at least:
(1) present invention utilizes Ni, Co, Mn, the K of tetra- kinds of elements of Cdsp(Ksp of Ni, Co, Mn, Cd distinguish this close characteristic
It is 2.0 × 10-15, 1.9 × 10-15, 1.6 × 10-13, 3.2 × 10-14), using Cd as modifying element.Using dehydrated alcohol as molten
Agent, nitrate as transition metal salt, using solvent-thermal method by four kinds of elements during solvent-thermal process under co-precipitation,
The cell positive material presoma of Ni-Co-Mn-Cd base is obtained, the ternary electricity of Cd is then mixed by the synthesis of high temperature solid-state roasting method
Pond positive electrode, preparation method is simple, at low cost.
(2) Cd is as a kind of inactive elemental with satisfactory electrical conductivity, is capable of the structure of stabilizing material after doping,
Improve the electronic conductivity of material.
(3) CdO carrier concentration with higher and Lacking oxygen, therefore be considered as a kind of n-type semiconductor, resistivity is
10-2-10-4Ω advantageously reduces the impedance of material.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 be embodiment 1, embodiment 2, embodiment 3, in reference examples 1 cell positive material XRD diffracting spectrum.
Fig. 2 is the SEM photograph of the cell positive material presoma in embodiment 1 under 0.01mol Cd doping.
Fig. 3 is the SEM photograph of the cell positive material in embodiment 1 under 0.01mol Cd doping.
Fig. 4 is the SEM photograph of the cell positive material presoma in embodiment 2 under 0.02mol Cd doping.
Fig. 5 is the SEM photograph of the cell positive material in embodiment 2 under 0.02mol Cd doping.
Fig. 6 is the SEM photograph of the cell positive material presoma in embodiment 3 under 0.03mol Cd doping.
Fig. 7 is the SEM photograph of the cell positive material in embodiment 3 under 0.03mol Cd doping.
Fig. 8 is the SEM photograph of the cell positive material presoma of the undoped Cd synthesized in reference examples 1.
Fig. 9 is the SEM photograph of the cell positive material of the undoped Cd synthesized in reference examples 1.
Figure 10 be embodiment 1, embodiment 2, embodiment 3, in reference examples 1 cell positive material charge-discharge property
Figure.
Figure 11 be embodiment 1, embodiment 2, embodiment 3, in reference examples 1 cell positive material Performance Analysis figure.
Figure 12 be embodiment 1, embodiment 2, embodiment 3, in reference examples 1 cell positive material high rate performance analysis chart.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution as follows will be further explained the technical solution, its implementation process and principle etc..
The modifying element palpus and Ni, Co, Mn in precursor synthesis stage have similar Ksp, can just make it in synthesis process in this way
Middle co-precipitation is got off, wherein the Ksp of Ni, Co, Mn, Cd are respectively 2.0 × 10-15, 1.9 × 10-15, 1.6 × 10-13, 3.2 ×
10-14, KspIt is close.Tetra- kinds of elements of Ni, Co, Mn and Cd are existed by solvent-thermal method using Cd as modifying element in the present invention
Co-precipitation is got off in solvent thermal reaction synthesis process, is synthesized the cell positive material presoma of Ni-Co-Mn-Cd base, is then led to
The cell positive material of Cd is mixed in the roasting synthesis of overmulling lithium.
As the one aspect of technical solution of the present invention, involved in be a kind of cell positive material presoma preparation
Method, comprising:
Ni base nitrate, Co base nitrate, Mn base nitrate and Cd base nitrate are dissolved in dehydrated alcohol, mixed
Close solution；
The mixed solution is subjected to solvent thermal reaction, makes Ni, Co, Mn and Cd element co-precipitation, and precipitate to obtaining
Object is post-processed, and the cell positive material presoma of Ni-Co-Mn-Cd base is obtained.
The present invention carries out doping vario-property in situ to material in the cell positive material precursor synthesis stage, and specific reaction is former
It manages shown in following equation:
7CH3CH2OH+4NO3 -→7CH3CHO+2NO↑+N2O+4OH-+5H2O； (1)
3Ni2++6OH-+2H2O→3Ni(OH)2·2H2O↓； (2)
2Co2++Mn2++6OH-→MnCo2O4↓+3H2O； (3)
Co2++2Mn2++6OH-→CoMn2O4↓+3H2O； (4)
Cd2++6OH-+2H2O→3Cd(OH)2·2H2O↓； (5)
In some embodiments, it specifically includes: the Ni (NO for being 0.1~0.3mol by summation3)2·6H2O、Co
(NO3)2·6H2O、Mn(NO3)2Aqueous solution and Cd (NO3)2·4H2O dissolves in 100~200mL dehydrated alcohol, obtains mixing molten
Liquid.
Wherein, it is preferably dissolved in 140~160mL dehydrated alcohol.
In some embodiments, in the mixed solution Ni, Co, Mn, Cd element molar ratio n (NixCoyMnz)∶nCd
=0.97~1: 0~0.03, wherein x+y+z=1, nCd ≠ 0.
In some more preferred embodiments, the molar ratio n of Ni, Co, Mn, Cd element in the mixed solution
(NixCoyMnz): nCd=0.98~1: 0~0.02, wherein x+y+z=1, nCd ≠ 0.
In some embodiments, the temperature of the solvent thermal reaction is 150~160 DEG C, and the time of solvent thermal reaction is
10~14h.
Wherein, mixed solution is placed in ptfe autoclave and carries out solvent thermal reaction.
In some embodiments, the post-processing specifically includes: using dehydrated alcohol by Ni, Co, Mn and Cd element
Sediment after co-precipitation washed once above, dry later, roasting.
In some more preferred embodiments, the temperature of the drying is 70~90 DEG C, and the time is 10~14h.
In some more preferred embodiments, the temperature of the roasting is 440~460 DEG C, and the time is 4~6h
The embodiment of the present invention also provides a kind of cell positive material presoma being prepared by preceding method.
As the other side of technical solution of the present invention, involved in be a kind of cell positive material preparation side
Method, comprising:
The cell positive material presoma is mixed with lithium salts, preroast and roasting is successively carried out later, obtains Cd
The cell positive material of doping.
In some embodiments, the temperature of the preroast is 480~520 DEG C, and the time is 4~6h.
In some embodiments, the temperature of the roasting is 830~870 DEG C, and the time is 9~12h.
In some embodiments, the mass ratio of the cell positive material presoma and lithium salts is 1: 1.03~1.06.
In some embodiments, the lithium salts includes lithium carbonate.
The embodiment of the present invention also provides a kind of cell positive material being prepared by preceding method.
In some specific embodiments, the preparation method of cell positive material, comprising:
S1, by summation be 0.2mol amount Ni (NO3)2·6H2O, Co (NO3)2·6H2O, Mn (NO3)2(50wt% is water-soluble
Liquid) and Cd (NO3)2·4H2O is dissolved in 150ml dehydrated alcohol according to suitable ratio respectively, obtains mixed solution；
S2, the mixed solution are stirred at room temperature up to being completely dissolved, and the solution is then divided into three parts and is moved on to
In the ptfe autoclave of three 100mL；The amount for the mixed solution being added in 100mL reaction kettle can control in reaction kettle
1/2 to the 2/3 of volume；
S3, reaction kettle, which are moved into baking oven, places 12h at 150~160 DEG C；
S4, finally with dehydrated alcohol by washing of precipitate 4 to 5 times, then will precipitating dry 12h at 80 DEG C in an oven, be
Make it that there is good pattern after high-temperature roasting, first roasts 5h at 450 DEG C in Muffle furnace before mixed lithium；
S5, the presoma and Li for adulterating Cd obtained in S42CO3It is uniformly mixed in 1: 1.05 ratio, is then placed in horse
The not first preroast 5h at 500 DEG C in furnace, and then roasts 10h at 850 DEG C, finally obtains the anode material of Cd doping
Material.
As the another aspect of technical solution of the present invention, involved in be cell positive material presoma above-mentioned or
Cell positive material above-mentioned is in preparing the application in lithium ion battery.
Below with reference to several preferred embodiments, further details of the technical solution of the present invention, it is clear that described
Embodiment be only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to the present invention
The range of protection.The test method of actual conditions is not specified in the following example, usually according to normal condition.
Embodiment 1
Adulterate precursor of lithium ionic cell positive material, the cell positive material (NCM-1), lithium-ion electric of 0.01mol Cd
The preparation and test method in pond, include the following:
(1) by 34.545852g Ni (NO3)2·6H2O, 11.524788g Co (NO3)2·6H2O, 14.17284g Mn
(NO3)2Cd (the NO of (50wt% aqueous solution) and 0.61692g3)2·4H2O is dissolved in 150ml dehydrated alcohol, the mixed solution
It is stirred at room temperature up to being completely dissolved, the solution is then divided into the polytetrafluoroethylene (PTFE) that three parts move on to three 100mL
In reaction kettle；Reaction kettle, which is moved into baking oven, places 12h at 150 DEG C；Finally with dehydrated alcohol by washing of precipitate 4 to 5 times, with
Precipitating is put into dry 12h at 80 DEG C in an oven afterwards, to make it that there is good pattern after high-temperature roasting, is mixed before lithium in Muffle
5h first is roasted at 450 DEG C in furnace, obtains the 622 cell positive material presomas that doping is 0.01mol Cd；
(2) by cell positive material presoma obtained and Li2CO3In mass ratio 1: 1.05 ratio is uniformly mixed, then
It is put into Muffle furnace the first preroast 5h at 500 DEG C, and then roasts 10h at 850 DEG C, finally obtaining doping is
Li (the Ni of 0.01mol Cd0.6Co0.2Mn0.2)0.99Cd0.01O2Cell positive material (NCM-1)；
(3) by Li (Ni obtained0.6Co0.2Mn0.2)0.99Cd0.01O2Cell positive material (NCM-1) and conductive black
The mixing of super P, binder PVDF 8: 1: 1 ratio uniforms in mass ratio, is added suitable -2 pyrrolidones ball milling of 1- methyl
15min is made into slurry and is uniformly coated on aluminium flake collector with coating machine, and 2 hours dry at 70 DEG C；Then vacuum is moved on to
Drying box is 12 hours dry at 120 DEG C, finally carries out tabletting, obtains electrode slice；
(4) using electrode slice obtained in step (3) as anode, lithium piece is used as to electrode, more sky thin polymer film conducts
Diaphragm (Celgard 2400), the LiPF of 1mol/L6The mixed liquor of and EC: DEC: EMC (volume ratio 1: 1: 1) is as electrolysis
Matter is assembled into button cell in glove box.
After tested, for the first time electric discharge of the cell positive material (NCM-1) under 0.1C multiplying power under 0.01mol Cd doping
Capacity is 186.3mAh/g, and capacity retention ratio can achieve 82.8% after recycling 100 times at 1C.
With X-ray diffraction (XRD) to cell positive material Li (Ni obtained0.6Co0.2Mn0.2)0.99Cd0.01O2(NCM-1)
X-ray diffraction is carried out, diffracting spectrum is as shown in Figure 1.
The SEM for adulterating the cell positive material presoma of 0.01mol Cd schemes as shown in Figure 2, can be clearly from figure
Presoma pattern is still spherical in shape out, and the petal-shaped of spherical surface starts to disappear, and surface starts to become fine and close, corresponding
The SEM figure of cell positive material is as shown in Figure 3.
As shown in Figure 10, cell positive material follows the charge-discharge property figure of cell positive material under 1C multiplying power under 0.1C
The cyclic curve that ring is 100 times is as shown in Figure 11.High rate performance curve under cell positive material different multiplying is as shown in Figure 12.
Embodiment 2
Adulterate precursor of lithium ionic cell positive material, the cell positive material (NCM-2), lithium-ion electric of 0.02mol Cd
The preparation and test method in pond, include the following:
(1) by 34.197g Ni (NO3)2·6H2O, 11.408g Co (NO3)2·6H2O, 14.0296g Mn (NO3)2
Cd (the NO of (50wt% aqueous solution) and 1.234g3)2·4H2O is dissolved in 100ml dehydrated alcohol, and the mixed solution is at room temperature
Then the solution is divided into three parts and moved on in the ptfe autoclave of three 100mL by stirring up to being completely dissolved；
Reaction kettle, which is moved into baking oven, places 10h at 150 DEG C；It, then will precipitating finally with dehydrated alcohol by washing of precipitate 4 to 5 times
Dry 14h at 70 DEG C in an oven is put first to exist in Muffle furnace before mixed lithium to make it that there is good pattern after high-temperature roasting
6h is roasted at 440 DEG C, obtains the 622 cell positive material presomas that doping is 0.02mol Cd；
(2) by cell positive material presoma obtained and Li2CO3In mass ratio 1: 1.03 ratio is uniformly mixed, then
It is put into Muffle furnace the first preroast 6h at 480 DEG C, and then roasts 9h at 830 DEG C, finally obtaining doping is 0.02mol
Li (the Ni of Cd0.6Co0.2Mn0.2)0.98Cd0.02O2Cell positive material (NCM-2)；
(3) by Li (Ni obtained0.6Co0.2Mn0.2)0.98Cd0.02O2Cell positive material (NCM-2) and conductive black
The mixing of super P, binder PVDF 8: 1: 1 ratio uniforms in mass ratio, is added suitable -2 pyrrolidones ball milling of 1- methyl
15min is made into slurry and is uniformly coated on aluminium flake collector with coating machine, and 2 hours dry at 70 DEG C；Then vacuum is moved on to
Drying box is 12 hours dry at 120 DEG C, finally carries out tabletting, obtains electrode slice；
(4) using electrode slice obtained in step (3) as anode, lithium piece is used as to electrode, more sky thin polymer film conducts
Diaphragm (Celgard 2400), the LiPF of 1mol/L6The mixed liquor of and EC: DEC: EMC (volume ratio 1: 1: 1) is as electrolysis
Matter is assembled into button cell in glove box.
After tested, for the first time discharge capacity of the cell positive material (NCM-2) of 0.02mol Cd doping under 0.1C multiplying power
For 179.5mAh/g, capacity retention ratio can achieve 81.8% after recycling 100 times at 1C.
With X-ray diffraction (XRD) to cell positive material Li (Ni obtained0.6Co0.2Mn0.2)0.98Cd0.02O2(NCM-2)
X-ray diffraction is carried out, diffracting spectrum is as shown in Figure 1.
The SEM for adulterating the cell positive material presoma of 0.02mol Cd schemes as shown in Figure 4, can be clearly from figure
Presoma pattern is still spherical in shape out, and the petal-shaped of spherical surface almost disappears, and surface starts to become very fine and close, relatively
The SEM figure for the cell positive material answered is as shown in Figure 5.
Charge-discharge property figure under 0.1C is as shown in Figure 10.Cell positive material is recycled for 100 times and is followed under 1C multiplying power
Ring curve is as shown in Figure 11.High rate performance curve under cell positive material different multiplying is as shown in Figure 12.
Embodiment 3
Adulterate precursor of lithium ionic cell positive material, the cell positive material (NCM-3), lithium-ion electric of 0.03mol Cd
The preparation and test method in pond, include the following:
(1) by 33.848g Ni (NO3)2·6H2O, 11.292g Co (NO3)2·6H2O, 14.887g Mn (NO3)2
Cd (the NO of (50wt% aqueous solution) and 1.851g3)2·4H2O is dissolved in 200ml dehydrated alcohol, and the mixed solution is at room temperature
Then the solution is divided into three parts and moved on in the ptfe autoclave of three 100mL by stirring up to being completely dissolved；
Reaction kettle, which is moved into baking oven, places 14h at 160 DEG C；It, then will precipitating finally with dehydrated alcohol by washing of precipitate 4 to 5 times
Dry 10h at 90 DEG C in an oven is put first to exist in Muffle furnace before mixed lithium to make it that there is good pattern after high-temperature roasting
4h is roasted at 460 DEG C, obtains the 622 cell positive material presomas that doping is 0.03mol Cd；
(2) by cell positive material presoma obtained and Li2CO3In mass ratio 1: 1.06 ratio is uniformly mixed, then
It is put into Muffle furnace the first preroast 4h at 520 DEG C, and then roasts 12h at 870 DEG C, finally obtaining doping is
Li (the Ni of 0.03mol Cd0.6Co0.2Mn0.2)0.97Cd0.03O2Cell positive material (NCM-3)；
(3) by Li (Ni obtained0.6Co0.2Mn0.2)0.97Cd0.03O2Cell positive material (NCM-3) and conductive black
The mixing of super P, binder PVDF 8: 1: 1 ratio uniforms in mass ratio, is added suitable -2 pyrrolidones ball milling of 1- methyl
15min is made into slurry and is uniformly coated on aluminium flake collector with coating machine, and 2 hours dry at 70 DEG C；Then vacuum is moved on to
Drying box is 12 hours dry at 120 DEG C, finally carries out tabletting, obtains electrode slice；
(4) using electrode slice obtained in step (3) as anode, lithium piece is used as to electrode, more sky thin polymer film conducts
The mixed liquor of diaphragm (Celgard 2400), the LiPF6 of 1 mol/L and EC: DEC: EMC (volume ratio 1: 1: 1) is as electrolysis
Matter is assembled into button cell in glove box.
After tested, for the first time discharge capacity of the cell positive material (NCM-3) of 0.03mol Cd doping under 0.1C multiplying power
For 166.1mAh/g, capacity retention ratio can achieve 67.3% after recycling 100 times at 1C.
With X-ray diffraction (XRD) to cell positive material Li (Ni obtained0.6Co0.2Mn0.2)0.97Cd0.03O2(NCM-3)
X-ray diffraction is carried out, diffracting spectrum is as shown in Figure 1.
The SEM for adulterating the cell positive material presoma of 0.03mol Cd schemes as shown in Figure 6, can be clearly from figure
Presoma pattern is still spherical in shape out, and the petal-shaped of spherical surface disappears, and surface becomes fine and close and with the presence of little particle, phase
The SEM figure of corresponding cell positive material is as shown in Figure 7.
Charge-discharge property figure under 0.1C is as shown in Figure 10.Cell positive material is recycled for 100 times and is followed under 1C multiplying power
Ring curve is as shown in Figure 11.High rate performance curve under cell positive material different multiplying is as shown in Figure 12.
Reference examples 1
The preparation side of cell positive material presoma, cell positive material, lithium ion battery in reference examples 1 and embodiment 1
Method is essentially identical, and difference is, the cell positive material presoma and cell positive material in reference examples 1 are undoped with Cd.
The system of precursor of lithium ionic cell positive material, cell positive material (NCM-P), lithium ion battery undoped with Cd
Standby and test method, include the following:
(1) by 34.8948g Ni (NO3)2·6H2O, 11.6412g Co (NO3)2·6H2O, 14.316g Mn (NO3)2
(50wt% aqueous solution) is dissolved in 150ml dehydrated alcohol, which is stirred at room temperature up to being completely dissolved, and then will
The solution is divided into three parts and moves on in the ptfe autoclave of three 100mL；Reaction kettle is moved into baking oven 150
12h is placed at DEG C；Finally with dehydrated alcohol by washing of precipitate 4 to 5 times, precipitating is then put into dry 12h at 80 DEG C in an oven,
To make it that there is good pattern after high-temperature roasting, 5h first is roasted at 450 DEG C in Muffle furnace before mixed lithium, is obtained undoped
The 622 cell positive material presomas of Cd；
(2) by cell positive material presoma obtained and Li2CO3It is uniformly mixed in 1: 1.05 ratio, is then placed in horse
The not first preroast 5h at 500 DEG C in furnace, and then roasts 10h at 850 DEG C, finally obtains undoped with Cd
LiNi0.6Co0.2Mn0.2O2Cell positive material (NCM-P)；
(3) by LiNi obtained0.6Co0.2Mn0.2O2Cell positive material (NCM-P) and conductive black super P, bonding
The mixing of agent PVDF 8: 1: 1 ratio uniforms in mass ratio is added suitable -2 pyrrolidones ball milling 15min of 1- methyl and is made into slurry use
Coating machine is evenly coated on aluminium flake collector, and 2 hours dry at 70 DEG C；Then vacuum oven is moved on to do at 120 DEG C
Dry 12 hours, tabletting is finally carried out, electrode slice is obtained；
(4) using electrode slice obtained in step (3) as anode, lithium piece is used as to electrode, more sky thin polymer film conducts
Diaphragm (Celgard 2400), the LiPF of 1mol/L6The mixed liquor of and EC: DEC: EMC (volume ratio 1: 1: 1) is as electrolysis
Matter is assembled into button cell in glove box.
After tested, undoped with the cell positive material LiNi of Cd0.6Co0.2Mn0.2O2(NCM-P) under 0.1C multiplying power
Discharge capacity is 173.2mAh/g for the first time, and capacity retention ratio is 69.3% after recycling 100 times at 1C.
With X-ray diffraction (XRD) to the cell positive material LiNi of undoped Cd obtained0.6Co0.2Mn0.2O2(NCM-
P X-ray diffraction) is carried out, diffracting spectrum is as shown in Figure 1, all diffraction maximums can be indexed to the layer with R-3m space group
Shape α-NaFeO2Structure.
The SEM figure of cell positive material presoma undoped with Cd as shown in Figure 8, can clearly find out forerunner from figure
Bodily form looks are spherical in shape, and spherical surface is in petal-shaped.The SEM figure of corresponding cell positive material is as shown in Figure 9.
Charge-discharge property figure under 0.1C is as shown in Figure 10.Cell positive material is recycled for 100 times and is followed under 1C multiplying power
Ring curve is as shown in Figure 11.High rate performance curve under cell positive material different multiplying is as shown in Figure 12.
Join shown in Fig. 1, it can be seen that adulterate the cell positive material (NCM-1) of 0.01 mol Cd in embodiment 1 and do not mix
The cell positive material LiNi of miscellaneous Cd0.6Co0.2Mn0.2O2(NCM-P) it compares, the two is not different, and illustrates that the doping of Cd does not change
Become the main structure of material.It adulterates in embodiment 2 and is adulterated in the cell positive material (NCM-2) and embodiment 3 of 0.02mol Cd
The cell positive material LiNi of the cell positive material (NCM-3) of 0.03mol Cd and undoped Cd0.6Co0.2Mn0.2O2(NCM-
P it) compares, the two illustrates that the doping of Cd does not influence material structure, but one small in 33 ° or so appearance without very big difference
Peak, the peak are corresponding with the crystal face of CdO.
Join shown in Figure 10, embodiment 1, embodiment 2, embodiment 3, in reference examples 1 cell positive material starting coulomb effect
Rate is followed successively by 86.09%, 85.18%, 85.56%, 84.39%.
Join shown in Figure 11, embodiment 1, embodiment 2, embodiment 3, in reference examples 1 cell positive material circulation conservation rate
82.8%, 81.8%, 67.3%, 69.3%.
Join be shown in Figure 12 embodiment 1, embodiment 2, embodiment 3, in reference examples 1 cell positive material high rate performance
Analysis chart, it is known that, the high rate performance in embodiment 1 and embodiment 2 under cell positive material different multiplying is better than electricity in reference examples 1
High rate performance under the positive electrode different multiplying of pond, however the high rate performance in embodiment 3 under cell positive material different multiplying
Lower than the high rate performance under cell positive material different multiplying in reference examples 1, this illustrate suitable Cd doped with being conducive to stablize
The structure of material improves the chemical property of material, but will lead to the content of inactive elemental in material when doping is excessively high
Rise, the diffusion of lithium ion is hindered, so that the chemical property of cell positive material can be deteriorated.
In addition, inventor also utilizes the alternate embodiments such as listed other raw materials and other process conditions above
Various raw materials and corresponding process conditions in 1-3 have carried out corresponding test, the content of required verifying and with embodiment 1-3 product
It is close.So do not explained one by one to the verifying content of each embodiment herein, only said using Examples 1 to 3 as representative
The bright excellent place of the present patent application.
It should be noted that, in this document, under normal circumstances, the element limited by sentence " including ... ", not
There is also other identical elements in including the steps that the element, process, method or experimental facilities for exclusion.
It should be appreciated that the above preferred embodiment is merely to illustrate the contents of the present invention, in addition to this, there are also other by the present invention
Embodiment, as long as those skilled in the art because of technical inspiration involved in the present invention, and use equivalent replacement or equivalent deformation
The technical solution that mode is formed is fallen within the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of cell positive material presoma characterized by comprising
Ni base nitrate, Co base nitrate, Mn base nitrate and Cd base nitrate are dissolved in dehydrated alcohol, obtain mixing molten
Liquid；
The mixed solution is subjected to solvent thermal reaction, makes Ni, Co, Mn and Cd element co-precipitation, and to obtained sediment into
Row post-processing, obtains the cell positive material presoma of Ni-Co-Mn-Cd base.
2. preparation method as described in claim 1, which is characterized in that specifically include: the Ni for being 0.1~0.3mol by summation
(NO3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2Aqueous solution and Cd (NO3)2·4H2O is in 100~200mL dehydrated alcohol
Dissolution, obtains mixed solution.
3. preparation method as described in claim 1, it is characterised in that: Ni, Co, Mn, Cd element rubs in the mixed solution
You are than n (NixCoyMnz): nCd=0.97~1: 0~0.03, wherein x+y+z=1, nCd ≠ 0；
Preferably, in the mixed solution Ni, Co, Mn, Cd element molar ratio n (NixCoyMnz): nCd=0.98~1: 0~
0.02, wherein x+y+z=1, nCd ≠ 0.
4. preparation method as described in claim 1, it is characterised in that: the temperature of the solvent thermal reaction is 150~160 DEG C,
The time of solvent thermal reaction is 10~14h.
5. preparation method as described in claim 1, which is characterized in that the post-processing specifically includes: using dehydrated alcohol
Sediment after Ni, Co, Mn and Cd element co-precipitation washed once to above, dry later, roasting；Preferably, described dry
Dry temperature is 70~90 DEG C, and the time is 10~14h；Preferably, the temperature of the roasting be 440~460 DEG C, the time be 4~
6h。
6. the cell positive material presoma being prepared by method of any of claims 1-5.
7. a kind of preparation method of cell positive material characterized by comprising
Cell positive material presoma described in claim 6 is mixed with lithium salts, successively carries out preroast and roasting later,
Obtain the cell positive material of Cd doping.
8. preparation method as claimed in claim 7, it is characterised in that: the temperature of the preroast is 480~520 DEG C, the time
For 4~6h；And/or the temperature of the roasting is 830~870 DEG C, the time is 9~12h；And/or the cell positive material
The mass ratio of presoma and lithium salts is 1: 1.03~1.06；And/or the lithium salts includes lithium carbonate.
9. the cell positive material that the method as described in any one of claim 7-8 is prepared.
10. cell positive material described in cell positive material presoma described in claim 6 or claim 9 is in system
Application in standby lithium ion battery.
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| CN112038640A (en) * | 2020-09-09 | 2020-12-04 | 浙江帕瓦新能源股份有限公司 | Porous carbon coated ternary positive electrode material and preparation method thereof |
| CN112510191A (en) * | 2020-12-02 | 2021-03-16 | 上海应用技术大学 | Cadmium-doped lithium ion battery ternary positive electrode material and modification method thereof |
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| US20040234857A1 (en) * | 2001-11-22 | 2004-11-25 | Ryuji Shiozaki | Positive electrode active material for lithium secondary cell and lithium secondary cell |
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| US20040234857A1 (en) * | 2001-11-22 | 2004-11-25 | Ryuji Shiozaki | Positive electrode active material for lithium secondary cell and lithium secondary cell |
| CN1667865A (en) * | 2004-03-12 | 2005-09-14 | 三星Sdi株式会社 | Lithium secondary battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112038640A (en) * | 2020-09-09 | 2020-12-04 | 浙江帕瓦新能源股份有限公司 | Porous carbon coated ternary positive electrode material and preparation method thereof |
| CN112510191A (en) * | 2020-12-02 | 2021-03-16 | 上海应用技术大学 | Cadmium-doped lithium ion battery ternary positive electrode material and modification method thereof |
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