CN103280569B - The rich lithium layer shape nickel ion doped of one kind graphene coated and preparation method and application - Google Patents
The rich lithium layer shape nickel ion doped of one kind graphene coated and preparation method and application Download PDFInfo
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- CN103280569B CN103280569B CN201310043005.8A CN201310043005A CN103280569B CN 103280569 B CN103280569 B CN 103280569B CN 201310043005 A CN201310043005 A CN 201310043005A CN 103280569 B CN103280569 B CN 103280569B
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Abstract
The present invention discloses the rich lithium layer shape nickel ion doped of a kind graphene coated and preparation method and application, and propylene liguid nitrile oligomer solution is stirred 8-72 hour by described preparation method at 80 ~ 300 DEG C, forms the LPAN solution of micro-cyclisation; A certain amount of anode material for lithium-ion batteries stratiform nickel ion doped powder is joined in the LPAN solution of micro-cyclisation, mixes; After stirring, at 80 DEG C, slow evaporation is complete; At 220 DEG C, full cross-linked; 750 ~ 900 DEG C of calcining 5-40 hour in last Muffle furnace in air atmosphere, the LPAN of micro-cyclisation forms class graphene-structured, be evenly distributed in lithium ion cell positive stratiform nickel ion doped material, thus obtain the anode material for lithium-ion batteries of class graphene coated rich lithium layer shape nickel ion doped.Described class graphene coated rich lithium layer shape nickel ion doped had both had higher structural stability and excellent chemical property, had again good stable circulation performance.
Description
Technical field
The present invention relates to chemical cell field, particularly relate to a kind graphene coated rich lithium layer shape nickel ion doped and preparation method thereof, described class graphene coated rich lithium layer shape nickel ion doped can be used for preparing anode material for lithium-ion batteries.
Background technology
In recent years, the new-energy automobile being core with new forms of energy power gets most of the attention.In various new forms of energy power form, lithium ion battery due to operating voltage high, specific energy is high, memory-less effect, pollution-free, and self discharge is little, has extended cycle life, and becomes the 21 century the most promising desirable energy.
The key of lithium ion battery development is the development of positive electrode.At present, the positive electrode that lithium ion battery is conventional mainly contains cobalt acid lithium, lithium nickelate, LiMn2O4 and LiFePO4.Wherein, it is good that LiMn2O4 has fail safe, and overcharge resistance performance is good, promoter manganese is abundant, cheap and non-toxic advantage, is the most rising positive electrode.LiMn2O4 mainly contains spinel-type LiMn
2o
4with stratiform LiMnO
2two types.Spinel-type LiMn
2o
4although fail safe is good, easily synthesizing, there is Jahn-Teller effect in it, and in charge and discharge process, easy recurring structure distortion, causes capacity to decay rapidly.Stratiform LiMnO
2be the positive electrode that new development is in recent years got up, there is price low, the advantage of specific capacity high (theoretical specific capacity 286mAh/g, actual specific capacity reaches more than 200mAh/g).Therefore, layered lithium manganate is one of industry crucial positive electrode of generally acknowledging the lithium ion battery with high energy density of most potentiality to be exploited, is the focus of research at present.
For stratiform LiMnO
2, the electrochemical behavior of desirable lamellar compound is more much better than osculant material.Research in the past shows, the stability of enhancing substance structure is improve stratiform LiMnO to reduce manganese dissolving in the electrolytic solution
2the key of chemical property.Researcher has carried out large quantity research, as adjustment synthesis technique, controls the granularity of product and surface area well, cationic doping vario-property etc.Wherein cationic doping is considered to improve stratiform LiMnO
2one of important channel of chemical property.The element suitable because adulterate and suitable dosage fundamentally can suppress the appearance of Jahn-Teller effect, stablize LiMnO
2layer structure, improves the cyclical stability of material.Ceder etc., by proposing element (as Ni, Co, Cr, Al, the Ca etc.) doping with other+3 valency after first principle calculation, can avoid changing to spinel structure, preparation stratiform LiMnO
2and take off in Li process in electrochemistry and stablize its layer structure.Although have received certain effect by adulterating, be entrained in while strengthening cyclical stability often with the decline of capacity.
Researcher find in research doping process degree of depth doping formed solid solution to formation and stable laminated structure very meaningful, further research also finds that the material list of rich lithium on the basis that doping forms solid solution reveals quite high structural stability and excellent chemical property.In the rich lithium layered cathode material developed at present, lamellar compound Li [(Ni
ymn
1-y)
1-xli
x] O
2due to the thermal stability that had and excellent chemical property, become the very promising positive electrode of one in new type lithium ion battery.
Although layered lithium manganate has plurality of advantages, also there is the defect of self, namely how to improve stratiform LiMnO
2the large high rate performance of larger capacity and battery is ensured while cycle performance.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind graphene coated rich lithium layer shape nickel ion doped and preparation method thereof, described class graphene coated rich lithium layer shape nickel ion doped, both there is higher structural stability and excellent chemical property, there is again good stable circulation performance, be intended to the defect problem solving layered lithium manganate existence.
Technical scheme of the present invention is as follows:
The preparation method of one kind graphene coated rich lithium layer shape nickel ion doped, wherein, the preparation method of described class graphene coated rich lithium layer shape nickel ion doped comprises the following steps:
Propylene liguid nitrile oligomer solution is stirred 8-72 hour at 80 ~ 300 DEG C, forms the propylene liguid nitrile oligomer solution of micro-cyclisation; Stratiform nickel ion doped powder is joined in the propylene liguid nitrile oligomer solution of micro-cyclisation, mixes; After stirring, at 80 DEG C, evaporation completely; At 220 DEG C, full cross-linked; 750 ~ 900 DEG C of calcining 5-40 hour in last Muffle furnace in air atmosphere, obtain described class graphene coated rich lithium layer shape nickel ion doped.
The preparation method of described class graphene coated rich lithium layer shape nickel ion doped, wherein, the mass ratio between described propylene liguid nitrile oligomer solution and stratiform nickel ion doped powder is (0.01-0.8): 1.
The preparation method of described class graphene coated rich lithium layer shape nickel ion doped, wherein, layered nickel ion doped powder is Li [(Ni
ymn
1-y)
1-cli
c] O
2, wherein, the scope of y is the scope of 0-1, c is 0-0.5.
The preparation method of described class graphene coated rich lithium layer shape nickel ion doped, wherein, layered nickel ion doped powder adopts following methods to obtain:
A. Ni (NO is used
3)
2with Mn (NO
3)
2for presoma, after adopting coprecipitation to be precipitated thing, in air atmosphere baking oven, abundant dried overnight obtains hybrid transition metal oxyhydroxide presoma [Ni
ymn
1-y] (OH)
2;
B. at room temperature by the M of certain mol proportion
a(OH)
b, [Ni
ymn
1-y] (OH)
2raw material fully grinds, and mixes, and after carrying out first sintering, cooling, grinding, then in Muffle furnace, carries out second time sintering, cooling, grinding in air atmosphere, obtains product rich lithium layer shape compound L i [(Ni
ymn
1-y)
1-cli
c] O
2positive electrode;
Wherein, described Ni (NO
3)
2with Mn (NO
3)
2between mol ratio be 1.1-10;
Described M
a(OH)
b[Ni
ymn
1-y] (OH)
2between mol ratio be (1.1-2.0): 1;
Described M
a(OH)
bmiddle M is Li, Na, K or Ca, and the scope of a is the scope of 1-2, b is 1-2.
The preparation method of described class graphene coated rich lithium layer shape nickel ion doped, wherein, in described steps A, the process that described employing coprecipitation is precipitated thing is by Ni (NO
3)
2with Mn (NO
3)
2mixed solution joins M
a(OH)
bthing is precipitated in solution.
The preparation method of described class graphene coated rich lithium layer shape nickel ion doped, wherein, in described steps A, described oven drying temperature is 150-300 DEG C, and the time is 10-20 hour.
The preparation method of described class graphene coated rich lithium layer shape nickel ion doped, wherein, in described step B, first sintering temperature is 400-600 DEG C, and the time is 2-6 hour; Second time sintering temperature is 500-1200 DEG C, and the time is 5-40 hour.
The preparation method of described class graphene coated rich lithium layer shape nickel ion doped, wherein, described propylene liguid nitrile oligomer solution solute used is propylene liguid nitrile oligomer, and the relative molecular weight of described propylene liguid nitrile oligomer is 106 ~ 100000; Solvent used is one or both combinations in water, methyl alcohol or ethanol; The concentration of described propylene liguid nitrile oligomer solution is 0.1 ~ 100%.
One kind graphene coated rich lithium layer shape nickel ion doped, wherein, described class graphene coated rich lithium layer shape nickel ion doped adopts the preparation method of class graphene coated as above rich lithium layer shape nickel ion doped to prepare.
A kind of class graphene coated as above rich lithium layer shape nickel ion doped, wherein, by described class graphene coated rich lithium layer shape nickel ion doped for the preparation of anode material for lithium-ion batteries.
Beneficial effect: the rich lithium layer shape nickel ion doped of a kind graphene coated provided by the present invention and preparation method and application, described class graphene coated rich lithium layer shape nickel ion doped can be used for preparing anode material for lithium-ion batteries.Described class graphene coated rich lithium layer shape nickel ion doped had both had higher structural stability and excellent chemical property, had again good stable circulation performance.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the class graphene coated rich lithium layer shape nickel ion doped material in embodiment of the present invention 1-4.
Fig. 2 is the enlarged drawing of part B in Fig. 1.
Fig. 3 is the enlarged drawing of C part in Fig. 1.
Fig. 4 is the stereoscan photograph of the class graphene coated rich lithium layer shape nickel ion doped material in the embodiment of the present invention 1.
Fig. 5 is the stereoscan photograph of the class graphene coated rich lithium layer shape nickel ion doped material in the embodiment of the present invention 2.
Fig. 6 is the stereoscan photograph of the class graphene coated rich lithium layer shape nickel ion doped material in the embodiment of the present invention 3.
Fig. 7 is the stereoscan photograph of the class graphene coated rich lithium layer shape nickel ion doped material in the embodiment of the present invention 4.
Fig. 8 is the cycle performance picture of the class graphene coated rich lithium layer shape nickel ion doped material in embodiment of the present invention 1-4.
Embodiment
The invention provides the rich lithium layer shape nickel ion doped of a kind graphene coated and preparation method and application, for making object of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The rich lithium layer shape nickel ion doped of a kind graphene coated provided by the present invention and preparation method and application, described class graphene coated rich lithium layer shape nickel ion doped is a kind of anode material for lithium-ion batteries.Described class graphene coated rich lithium layer shape nickel ion doped had both had higher structural stability and excellent chemical property, had again good stable circulation performance.
The preparation method of class graphene coated of the present invention rich lithium layer shape nickel ion doped, is that propylene liguid nitrile oligomer solution is stirred 8-72 hour at 80 ~ 300 DEG C, forms the LPAN solution of micro-cyclisation; A certain amount of anode material for lithium-ion batteries stratiform nickel ion doped powder is joined in the LPAN solution of micro-cyclisation, mixes; After stirring, at 80 DEG C, slow evaporation is complete; At 220 DEG C, full cross-linked; 750 ~ 900 DEG C of calcining 5-40 hour in last Muffle furnace in air atmosphere, the LPAN of micro-cyclisation forms class graphene-structured, be evenly distributed in lithium ion cell positive stratiform nickel ion doped material, thus obtain the anode material for lithium-ion batteries of class graphene coated rich lithium layer shape nickel ion doped.
Particularly, the preparation method of described class graphene coated rich lithium layer shape nickel ion doped is as follows:
A. Ni (NO is used
3)
2with Mn (NO
3)
2for presoma, after adopting coprecipitation to be precipitated thing, fully dry in air atmosphere, obtain the presoma [Ni of hybrid transition metal oxyhydroxide
ymn
1-y] (OH)
2;
B. at room temperature by the M of certain mol proportion
a(OH)
b, [Ni
ymn
1-y] (OH)
2abundant grinding, mixes; Carry out first sintering, cooling, grinding in air atmosphere after, then in Muffle furnace, carry out second time sintering, cooling, grinding, obtain product rich lithium layer shape compound L i [(Ni
ymn
1-y)
1-cli
c] O
2positive electrode;
C. by liquid polypropylene nitrile (LPAN) dispersion in a solvent after, then with rich lithium layer shape compound L i [(Ni
ymn
1-y)
1-cli
c] O
2be uniformly mixed in the liquid phase, and then slow evaporation is dry; Finally obtain class graphene coated rich lithium layer shape nickel ion doped with two sections of solid phase method sintering.
Wherein, in described steps A, described Ni (NO
3)
2with Mn (NO
3)
2between mol ratio be 1.1-10; Described presoma [Ni
ymn
1-y] (OH)
2in, the scope of y is 0-1.Described coprecipitation is by Ni (NO
3)
2with Mn (NO
3)
2mixed solution slowly joins M
a(OH)
bthing is precipitated in solution.The process of described drying is carried out in an oven, and dry temperature is 150-300 DEG C, and the time is 10-20 hour.
Wherein, described steps A is specially: by Ni (NO
3)
2with Mn (NO
3)
2mixed solution slowly joins M
a(OH)
bthing is precipitated in solution; Filtering precipitate, after rinsing sediment 2-3 time, sediment dried overnight at 150-300 DEG C of temperature, obtains hybrid transition metal oxyhydroxide presoma [Ni
ymn
1-y] (OH)
2.
In described step B, described M
a(OH)
bmiddle M is Li, Na, K or Ca etc., and the scope of a is the scope of 1-2, b is 1-2; Described M
a(OH)
bbe preferably LiOHH
2o.Described M
a(OH)
b[Ni
ymn
1-y] (OH)
2the mol ratio of raw material is: (1.1-2.0): 1.Described rich lithium layer shape compound L i [(Ni
ymn
1-y)
1-cli
c] O
2in, the scope of c is: 0-0.5.In described first sintering process, sintering temperature is 400-600 DEG C, and the time is 2-6 hour; In second time sintering process, temperature is 500-1200 DEG C, and the time is 5-40 hour.
In described step C, described liquid polypropylene nitrile (LPAN) and rich lithium layer shape compound L i [(Ni
ymn
1-y)
1-cli
c] O
2mixing, ratio is in mass ratio: (0.01-0.8): 1.In the described process mixed, its hybrid mode is for stirring or ball milling.
Wherein, described propylene liguid nitrile oligomer solution solute used is propylene liguid nitrile oligomer, and its relative molecular weight is 106 ~ 100000; Solvent used is one or both combinations in water, methyl alcohol or ethanol, and the concentration of propylene liguid nitrile oligomer solution is 0.1 ~ 100%.Described propylene liguid nitrile oligomer can also be acrylonitrile homopolymer, also can be the copolymer with other vinyl monomer, and other vinyl monomer is styrene, methyl methacrylate, hydroxyethyl methacrylate, acrylic acid, methylene-succinic acid.
Also provide the class graphene coated rich lithium layer shape nickel ion doped adopting the preparation method of above-mentioned class graphene coated rich lithium layer shape nickel ion doped to prepare in the present invention, described class graphene coated rich lithium layer shape nickel ion doped can be used for making anode material for lithium-ion batteries.
Below by embodiment, illustrate outstanding feature of the present invention and marked improvement further, be only the present invention is described and never limits the present invention.
Embodiment 1
A. by the Ni (NO of 50 milliliters
3)
2with Mn (NO
3)
2mixed solution slowly joins the LiOHH of 400 milliliters
2be precipitated in O solution.Filter, after the flushes sediment that obtains 2-3 time, sediment, 180 DEG C of dried overnight, obtains hybrid transition metal oxyhydroxide presoma [Ni
0.5mn
0.5] (OH)
2.
B. raw material Li OHH is taken by setting 1.1:1
2o, [Ni
0.5mn
0.5] (OH)
2, at room temperature raw material is fully ground, mixes, carry out first sintering (400 DEG C, 6 hours), cooling, grinding in air atmosphere after, then in Muffle furnace, carry out second time sintering (1200 DEG C, 5 hours), cooling, grinding, obtain product rich lithium layer shape compound L i [(Ni
0.5mn
0.5)
0.9li
0.1] O
2positive electrode.
C. by 5g10%LPAN(molecular weight 1600) solution (mass percent) heats 20 hours, forms the LPAN solution of micro-cyclisation, then add 10gLi [(Ni at 120 DEG C
0.5mn
0.5)
0.9li
0.1] O
2powder, complete at 80 DEG C of slow evaporations after stirring, then in an oven 220 DEG C full cross-linked, then in Muffle furnace 780 DEG C of calcining 10h, obtain the Li [(Ni of class graphene coated
0.5mn
0.5)
0.9li
0.1] O
2powdery positive electrode.Its XRD schemes as shown in Fig. 1 ~ Fig. 3, and stereoscan photograph as shown in Figure 4.
Embodiment 2
A. by the Ni (NO of 50 milliliters
3)
2with Mn (NO
3)
2mixed solution slowly joins the LiOHH of 400 milliliters
2be precipitated in O solution.Filter, after the flushes sediment that obtains 2-3 time, sediment, 180 DEG C of dried overnight, obtains hybrid transition metal oxyhydroxide presoma [Ni
0.3mn
0.7] (OH)
2.
B. raw material Li OHH is taken by setting 1.15:1
2o, [Ni
0.3mn
0.7] (OH)
2at room temperature raw material is fully ground, mix, first sintering (500 DEG C is carried out in air atmosphere, 4 hours), cooling, grinding after, in Muffle furnace, carry out second time sintering (1000 DEG C, 20 hours), cooling, grinding again, obtain product rich lithium layer shape compound L i [(Ni
0.3mn
0.7)
0.85li
0.15] O
2positive electrode.
C. by 5g10%LPAN(molecular weight 1600) solution (mass percent) heats 20 hours, forms the LPAN solution of micro-cyclisation, then add 10gLi [(Ni at 120 DEG C
0.3mn
0.7)
0.85li
0.15] O
2powder, complete at 80 DEG C of slow evaporations after stirring, then in an oven 220 DEG C full cross-linked, then in Muffle furnace 820 DEG C of calcining 10h, obtain the Li [(Ni of class graphene coated
0.3mn
0.7)
0.85li
0.15] O
2powdery positive electrode.Its XRD schemes as shown in Fig. 1 ~ Fig. 3, and stereoscan photograph as shown in Figure 5.
Embodiment 3
A. by the Ni (NO of 50 milliliters
3)
2with Mn (NO
3)
2mixed solution slowly joins the LiOHH of 400 milliliters
2be precipitated in O solution.Filter, after the flushes sediment that obtains 2-3 time, sediment, 180 DEG C of dried overnight, obtains hybrid transition metal oxyhydroxide presoma [Ni
0.4mn
0.6] (OH)
2.
B. raw material Li OHH is taken by setting 1.2:1
2o, [Ni
0.4mn
0.6] (OH)
2at room temperature raw material is fully ground, mix, carry out first sintering (600 DEG C, 2 hours), cooling, grinding in air atmosphere after, then in Muffle furnace, carry out second time sintering (500 DEG C, 40 hours), cooling, grinding, obtain product rich lithium layer shape compound L i [(Ni
0.4mn
0.6)
0.9li
0.1] O
2positive electrode.
C. by 5g10%LPAN(molecular weight 1600) solution (mass percent) heats 20 hours, forms the LPAN solution of micro-cyclisation, then add 10gLi [(Ni at 120 DEG C
0.4mn
0.6)
0.9li
0.1] O
2powder, complete at 80 DEG C of slow evaporations after stirring, then in an oven 220 DEG C full cross-linked, then in Muffle furnace 850 DEG C of calcining 10h, obtain the Li [(Ni of class graphene coated
0.4mn
0.6)
0.9li
0.1] O
2powdery positive electrode.Its XRD schemes as shown in Fig. 1 ~ Fig. 3, and stereoscan photograph as shown in Figure 6.
Embodiment 4
A. by the Ni (NO of 50 milliliters
3)
2with Mn (NO
3)
2mixed solution slowly joins the LiOHH of 400 milliliters
2be precipitated in O solution.Filter, after the flushes sediment that obtains 2-3 time, sediment, 180 DEG C of dried overnight, obtains hybrid transition metal oxyhydroxide presoma [Ni
0.6mn
0.4] (OH)
2.
B. raw material Li OHH is taken by setting 1.25:1
2o, [Ni
0.6mn
0.4] (OH)
2, at room temperature raw material is fully ground, mixes, carry out first sintering (450 DEG C, 6 hours), cooling, grinding in air atmosphere after, then in Muffle furnace, carry out second time sintering (750 DEG C, 15 hours), cooling, grinding, obtain product rich lithium layer shape compound L i [(Ni
0.6mn
0.4)
0.9li
0.1] O
2positive electrode.
C. by 5g10%LPAN(molecular weight 1600) solution (mass percent) heats 20 hours, forms the LPAN solution of micro-cyclisation, then add 10gLi [(Ni at 120 DEG C
0.6mn
0.4)
0.9li
0.1] O
2powder, complete at 80 DEG C of slow evaporations after stirring, then in an oven 220 DEG C full cross-linked, then in Muffle furnace 900 DEG C of calcining 10h, obtain the Li [(Ni of class graphene coated
0.6mn
0.4)
0.9li
0.1] O
2powdery positive electrode.Its XRD schemes as shown in Fig. 1 ~ Fig. 3, and stereoscan photograph as shown in Figure 7.
According to above-described embodiment, positive electrode prepared by the routine 1-4 of further employing carries out battery preparation and battery performance test: in active material: acetylene black: the ratio (mass percent) that adhesive equals 80:10:10 is mixed and made into cathode film, using lithium sheet as negative pole, using Cellgard2300 perforated membrane as barrier film, with 1molL
-1liPF
6/ EC+DMC (volume ratio 1:1) mixed solution makes electrolyte, is assembled into button cell.LandBS9300 (Wuhan gold promise electronics) program control automatic electrochemical test carries out electrochemical property test.Wherein, the cycle performance figure of the rich lithium layer shape of the class graphene coated in embodiment 1 ~ 4 nickel ion doped material as shown in Figure 8.
When current density is 0.1C, its specific discharge capacity is 200-270mAh/g, and its specific discharge capacity after 100 times that circulates still remains on 97%.Concrete outcome is as shown in table 1.
Table 1 example 1-4 do the chemical property of battery prepared by positive electrode
| Embodiment is numbered | Initial discharge specific capacity (mAh/g) | To circulate 50 capability retentions (%) |
| Embodiment 1 | 278.8 | 97.9 |
| Embodiment 2 | 105.0 | 98.2 |
| Embodiment 3 | 230.0 | 98.6 |
| Embodiment 4 | 246.1 | 98.8 |
As can be seen from the embodiment of the present invention 1 ~ 4, the class graphene coated rich lithium layer shape nickel ion doped of gained had both had higher structural stability and excellent chemical property, there is again good stable circulation performance, efficiently solve the defect existing for existing stratiform manganate cathode material for lithium.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection range that all should belong to claims of the present invention.
Claims (7)
1. the preparation method of a kind graphene coated rich lithium layer shape nickel ion doped, is characterized in that, the preparation method of described class graphene coated rich lithium layer shape nickel ion doped comprises the following steps:
Propylene liguid nitrile oligomer solution is stirred 8-72 hour at 80 ~ 300 DEG C, forms the propylene liguid nitrile oligomer solution of micro-cyclisation; Stratiform nickel ion doped powder is joined in the propylene liguid nitrile oligomer solution of micro-cyclisation, mixes; After stirring, at 80 DEG C, evaporation completely; At 220 DEG C, full cross-linked; 750 ~ 900 DEG C of calcining 5-40 hour in last Muffle furnace in air atmosphere, obtain described class graphene coated rich lithium layer shape nickel ion doped;
Mass ratio between described propylene liguid nitrile oligomer solution and stratiform nickel ion doped powder is (0.01-0.8): 1;
Layered nickel ion doped powder is Li [(Ni
ymn
1-y)
1-cli
c] O
2, wherein, the scope of y is the scope of 0-1, c is 0-0.5;
Layered nickel ion doped powder adopts following methods to obtain:
A. Ni (NO is used
3)
2with Mn (NO
3)
2for presoma, after adopting coprecipitation to be precipitated thing, dry at air atmosphere, obtain hybrid transition metal oxyhydroxide presoma [Ni
ymn
1-y] (OH)
2;
B. at room temperature by the M of certain mol proportion
a(OH)
b, [Ni
ymn
1-y] (OH)
2raw material fully grinds, and mixes; Carry out first sintering, cooling, grinding in air atmosphere after, then in Muffle furnace, carry out second time sintering, cooling, grinding, obtain product rich lithium layer shape compound L i [(Ni
ymn
1-y)
1-cli
c] O
2positive electrode;
Wherein, described Ni (NO
3)
2with Mn (NO
3)
2between mol ratio be 1.1-10;
Described M
a(OH)
b[Ni
ymn
1-y] (OH)
2between mol ratio be (1.1-2.0): 1;
Described M
a(OH)
bfor LiOHH
2o.
2. the preparation method of class graphene coated according to claim 1 rich lithium layer shape nickel ion doped, it is characterized in that, in described steps A, the process that described employing coprecipitation is precipitated thing is by Ni (NO
3)
2with Mn (NO
3)
2mixed solution joins M
a(OH)
bthing is precipitated in solution.
3. the preparation method of class graphene coated according to claim 1 rich lithium layer shape nickel ion doped, it is characterized in that, in described steps A, in described dry run, temperature is 150-300 DEG C, and the time is 10-20 hour.
4. the preparation method of class graphene coated according to claim 1 rich lithium layer shape nickel ion doped, it is characterized in that, in described step B, described first sintering temperature is 400-600 DEG C, and the time is 2-6 hour; Second time sintering temperature is 500-1200 DEG C, and the time is 5-40 hour.
5. the preparation method of class graphene coated according to claim 1 rich lithium layer shape nickel ion doped, it is characterized in that, described propylene liguid nitrile oligomer solution solute used is propylene liguid nitrile oligomer, and the relative molecular weight of described propylene liguid nitrile oligomer is 106 ~ 100000; Solvent used is one or both combinations in water, methyl alcohol or ethanol; The mass concentration of described propylene liguid nitrile oligomer solution is 0.1 ~ 100%.
6. a kind graphene coated rich lithium layer shape nickel ion doped, is characterized in that, described class graphene coated rich lithium layer shape nickel ion doped adopts the preparation method of the rich lithium layer shape of the class graphene coated as described in any one of claim 1 ~ 5 nickel ion doped to prepare.
7. a class graphene coated as claimed in claim 6 rich lithium layer shape nickel ion doped, is characterized in that, by described class graphene coated rich lithium layer shape nickel ion doped for the preparation of anode material for lithium-ion batteries.
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| CN111599999B (en) * | 2020-05-25 | 2022-04-08 | 蜂巢能源科技股份有限公司 | Cobalt-free cathode material, preparation method thereof and lithium ion battery |
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| CN102263239A (en) * | 2011-06-21 | 2011-11-30 | 刘剑洪 | Graphene-like clad and doped lithium manganate composite cathode material and preparation method |
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