CN103137976A - Nanometer composite material and preparation method thereof, positive electrode material and battery - Google Patents
Nanometer composite material and preparation method thereof, positive electrode material and battery Download PDFInfo
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- CN103137976A CN103137976A CN2011103804792A CN201110380479A CN103137976A CN 103137976 A CN103137976 A CN 103137976A CN 2011103804792 A CN2011103804792 A CN 2011103804792A CN 201110380479 A CN201110380479 A CN 201110380479A CN 103137976 A CN103137976 A CN 103137976A
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Abstract
The present invention provides a nanometer composite material, which contains a lithium element and a transition metal element, wherein the lithium element is from a lithium salt and/or a lithium oxide, the transition metal element is from a transition metal and/or a transition metal oxide, and a molar ratio of the lithium element to the transition metal element is 0.25-8:1, preferably 1-4:1. The present invention further provides a preparation method for the nanometer composite material, a secondary lithium battery positive electrode material containing the nanometer composite material, and a secondary lithium battery containing the nanometer composite material.
Description
Technical field
The present invention relates to a kind of nano composite material and its preparation method and application, relate to particularly a kind of lithium-transition metal nano composite material and preparation method thereof, and the serondary lithium battery that comprises described nano composite material is with positive electrode and serondary lithium battery.
Background technology
At present, commercial lithium-ion batteries generally adopts LiCoO
2Anodal, LiMn
2O
4Anodal, LiFePO
4Positive pole and graphitized carbon negative material.There is certain irreversible capacity loss in graphitized carbon material in all charge and discharge cycles of head, cause first all coulombic efficiencies of this full battery system only can reach approximately 92%.In addition, because many limiting factors of graphitized carbon material negative pole are (as lower in specific capacity, high-rate charge-discharge capability is relatively poor, easily form dendrite at surperficial precipitating metal lithium and cause short circuit etc.), the new material of the high lithium storage content that exploitation embedding lithium current potential is higher is the focus of present negative material research and development, comprise the alloy type negative material, as material stanniferous, silicon; The transistion metal compound negative material, as contain the transistion metal compound of Mn, Cr, Fe, Ni, Co; The transistion metal compound material that contains lithium is as LiVO
2, LiTiO
2The nontransition metal compound-material is as SnO
2, SnO, Sb
2O
3Deng.But all there is a defective in these high power capacity negative materials, namely after first all embedding lithiums to take off in the lithium process irreversible capacity larger.Therefore, when using this class material, can cause first all coulombic efficiencies of full battery system further to reduce.
In order to solve the inefficient problem of negative pole initial charge/discharge, successively propose in prior art directly to add in positive pole and add lithium metal, positive pole in lithium metal, negative pole and add the lithium, the negative pole that contain sealer and add the lithium, the negative pole that contain sealer and add and contain the compound of lithium (as Li
xTMN
y, TM=Co, Fe, Ni, Cu) or the method such as lithium alloy.But be unstable character because these add material in air, have in actual applications certain technical difficulty, such as have a series of safety problems etc. in the processes such as electrode fabrication, battery assembling.
Summary of the invention
Therefore, the object of the invention is to overcome the inefficient defective of present negative pole initial charge/discharge, avoid simultaneously the potential safety hazard that causes because directly adding the materials such as lithium metal, provide a kind of irreversible capacity that can effectively reduce or eliminate negative pole in the first all charge and discharge cycles of full battery system, with the lithium that improves enclosed pasture efficient of first week of battery-transition metal nano composite material and its preparation method and application.
The invention provides a kind of nano composite material, described nano composite material comprises elemental lithium and transition metal, and wherein, described elemental lithium can be from the oxide of lithium salts and/or lithium; Described transition metal can be from the oxide of transition metal and/or transition metal; The mol ratio of described elemental lithium and transition metal can be 0.25～8: 1, can be preferably 1～4: 1.
According to nano composite material of the present invention, wherein, the average grain diameter of the oxide of described lithium salts, lithium, transition metal and transition metal oxide can be 1～100nm independently of one another, is preferably 1～50nm.
According to nano composite material of the present invention, wherein, described lithium salts can be one or more in lithium carbonate, lithium oxalate and lithium acetate, is preferably lithium carbonate; The oxide of described lithium can be lithium peroxide or lithia; Described transition metal can be Ti, Cu, Mn, Fe, Co, Ni, Zn, Ag, Zr, Nb, one or more in Mo and W; Described transition metal oxide can be M
aO
z, wherein M is Ti, Cu, Mn, Fe, Co, Ni, Zn, Ag, Zr, Nb, Mo or W, a=0.5～3, z=0.5～5.
According to nano composite material of the present invention, wherein, the surface of described nano composite material can be coated with carbon-coating and/or inert compound layer.
According to nano composite material of the present invention, wherein, described carbon-coating can be graphitized carbon or ungraphitised carbon; The thickness of described carbon-coating can be 0.4～100nm, is preferably 1～10nm; Described inert compound can be Al
2O
3, TiO
2, ZrO
2, ZnO, HfO
2, SiO
2, MgO, AlPO
4, AlF
3And ZrO
2In one or more; The thickness of described inert compound layer can be 0.4～100nm, is preferably 1～10nm.
According to nano composite material of the present invention, wherein, described nano composite material can for subsphaeroidal dusty material, filamentary material, club-shaped material, thin-film material or aperture be 1～100nm contain the hole material, be preferably subsphaeroidal dusty material.
The present invention also provides a kind of method for preparing nano composite material of the present invention, and described preparation method can comprise chemical method or Physical;
Described chemical method comprises: preparation contains the mixed solution of lithium salts and transition metal salt, adds ammonium bicarbonate soln when stirring in mixed solution, and the mol ratio of described transition metal salt, lithium salts and carbonic hydroammonium is 1: 1～2: 2～4; After fully stirring under 50～100 ℃ standing 1～96 hour, after drying, products therefrom is ground, roasting, namely obtain nano composite material;
Described Physical comprises: the oxide of lithium salts and/or lithium is mixed with transition metal and/or transition metal oxide, fully grind and obtain nano composite material.
Preparation in accordance with the present invention, wherein, in described chemical method, described lithium salts can be lithium acetate, lithium oxalate, lithium chloride or lithium nitrate; Described transition metal salt can be acetate, oxalates, chlorate or the nitrate of transition metal; The described well-beaten time can be 1～24h; Described roasting condition can under air atmosphere in 400～600 ℃ of roasting 1～10h.
Preparation in accordance with the present invention, wherein, described preparation method also is included in the step of coated with carbon bed and/or the inert compound layer of described nano composite material.The method of described coating carbon-coating and/or inert compound can for:
Described nano composite material is mixed with the precursor of carbon, in pyrolysis in inert atmosphere or reducing atmosphere under 300～1000 ℃, make its coated with carbon bed; And/or
Described nano composite material is adopted chemical vapour deposition technique, make organic gas in pyrolysis in inert atmosphere or reducing atmosphere under 300～1000 ℃, make its coated with carbon bed; And/or
Described nano composite material is put into ionic liquid or contain organic solution and form slurry like material, then pyrolysis in inert atmosphere or reducing atmosphere makes its coated with carbon bed; And/or
Described nano composite material is adopted metal organic chemical compound vapor deposition method, atomic layer deposition method, sol-gal process or spray drying process, make its surface coat the inert compound layer.
The present invention provides again a kind of serondary lithium battery positive electrode, and wherein, described positive electrode comprises nano composite material of the present invention.
According to positive electrode of the present invention, wherein, described nano composite material can account for 1～30wt% of positive electrode total weight, is preferably 5～16wt%; The positive active material of described positive electrode is selected from LiCoO
2, LiMn
2O
4, LiNi
1/3Co
1/3Mn
1/3O
2, LiFePO
4, xLi
2MnO
3(1-x) LiMO
2Or LiNi
0.5Mn
1.5O
4
The present invention also provides a kind of serondary lithium battery, and wherein, the positive pole of described serondary lithium battery comprises nano composite material of the present invention and/or positive electrode.Described serondary lithium battery can be used for all kinds of mobile electronic devices or fixed power-supply device, fields such as mobile phone, notebook computer, portable video recorder, electronic toy, electric tool, electric automobile, hybrid electric vehicle, electric topedo, electronic toy, accumulation power supply, and be not limited to this.
The present invention has following beneficial effect:
(1) lithium provided by the invention-transition metal nano composite material can make by very easy method, and raw material and manufacturing cost are all lower, are easy to large-scale production.
When (2) nano composite material provided by the invention was charged in first week of battery, charging capacity can reach 100～400mAh/g, and discharge capacity is less than 10mAh/g, therefore be suitable as very much the additive of positive electrode, irreversibly provide excessive lithium ion in the circulation of the first week, compensate the irreversible capacity of lithium cell cathode material.
(3) nano composite material of the present invention, with lithium metal, compare through the interpolations materials such as lithium metal, lithium alloys of protection, stable chemical nature, security performance is high, is convenient to store and use.
Description of drawings
Below, describe by reference to the accompanying drawings embodiment of the present invention in detail, wherein:
Fig. 1 a and Fig. 1 b show the nickel oxide of the embodiment of the present invention 1 preparation and the field emission scanning electron microscope photo of lithium carbonate nano composite material;
Fig. 2 shows the nickel oxide of the embodiment of the present invention 1 preparation and the X ray diffracting spectrum of lithium carbonate nano composite material;
Fig. 3 shows the nickel oxide of the embodiment of the present invention 1 preparation and the last fortnight charging and discharging curve of lithium carbonate nano composite material;
The X ray diffracting spectrum when nickel oxide that Fig. 4 shows the embodiment of the present invention 1 preparation charges to 4.5V, 4.8V week with lithium carbonate nano composite material and head thereof; Wherein, curve 1), curve 2) and curve 3) represent respectively described nano composite material before charging, charge to 4.5V, the collection of illustrative plates when charging to 4.8V;
Fig. 5 shows first three all charging and discharging curve of commercial Spinel lithium manganese oxygen positive electrode;
The nickel oxide that Fig. 6 shows the embodiment of the present invention 1 preparation mixed first three all charging and discharging curve of the positive electrode of rear preparation by weight 1: 1 with commercial Spinel lithium manganese oxygen positive electrode with the lithium carbonate nano composite material.
Embodiment
Further illustrate the present invention below by specific embodiment, still, should be understood to, these embodiment are only used for the use that specifically describes more in detail, and should not be construed as for limiting in any form the present invention.
General description is carried out to the material and the test method that use in the present invention's test in this part.Although for to realize that many materials and method of operation that the object of the invention is used are well known in the art, the present invention still does to describe in detail as far as possible at this.It will be apparent to those skilled in the art that in context, if do not specify, material therefor of the present invention and method of operation are well known in the art.
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Take 0.025mol nickel acetate (Ni (CH
3COO)
24H
2O) and 0.05mol lithium acetate (CH
3COOLi2H
2O), join in the container of the deionized water that contains 100 milliliters, be stirred to the solution clarification, then under strong agitation, dropwise splash into the aqueous solution that contains 0.075mol carbonic hydroammonium.In this process, solution becomes green suspension-turbid liquid gradually by green settled solution.After fully stirring 1 hour again, resulting green suspension-turbid liquid is kept approximately 72h in the constant temperature oven of 80 ℃, to the complete evaporate to dryness of green suspension-turbid liquid, obtain green gel shape material this moment.
This green gel shape substance transfer to ball mill, is obtained dusty material after grinding about half an hour.This dusty material is placed in Muffle furnace, 400 ℃ of roastings 1 hour, can obtains NiO-Li of the present invention
2CO
3Nano composite material is denoted as A1.
The field emission scanning electron microscope of product A 1 (S-4800, Hitachi, Ltd, Japan, 10 kilovolts of accelerating voltages) photo as shown in Figure 1, as seen the primary particle of product is approximated to spherically, and average grain diameter is about 20～50nm, and numerous such primary particles are reunited and formed micron-sized second particle.The X ray diffracting spectrum of A1 (X ' Pert Pro MPD, PHILIPS Co., Holland) as shown in Figure 2, the main component of visible product is Li
2CO
3, NiO and metal Ni.In analysis of chemical elements result demonstration product A 1, the mol ratio of elemental lithium and nickel element is 2: 1.
With the n-formyl sarcolysine base pyrrolidone solution of A1 and acetylene black (AB) and 10% Kynoar (PVDF) at normal temperatures and pressures the mixed-shaped form slurry (weight ratio is A1: acetylene black: PVDF=80: 10: 10), evenly be coated on aluminum substrates, then dry 5h under 60 ℃, the film of gained is compressed under 10MPa pressure, then it is cut into the electrode slice of 8 * 8mm as the positive pole of simulated battery.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is 1mol LiPF
6Be dissolved in the mixed solvent of 1L EC (ethylene carbonate) and DMC (dimethyl carbonate) (the solvent volume ratio is 1: 1).Positive pole, negative pole, electrolyte, barrier film are assembled into simulated battery in the glove box of argon shield.
The electro-chemical test step of simulated battery:
At first charge to 4.5V with 10mA/g, then be discharged to 2.0V with 10mA/g, then repeat successively this two processes, its charging and discharging capacity to the curve of voltage as shown in Figure 3.Can find out, the positive pole specific capacity in initial charge process prepared with A1 can reach 240mAh/g (referring to table 1), and the specific capacity in discharge process first is only 8mAh/g.Therefore its irreversible capacity is very high, can irreversibly provide excessive lithium ion in the circulation of the first week, compensates the negative pole lithium ion that irreversible reaction consumes in first Zhou Xunhuan.
The positive pole that A1 is prepared charge to after 4.5V and 4.8V X ray diffracting spectrum as shown in Figure 4.As can be seen from the figure, after charging, the Li in material
2CO
3Corresponding diffraction peak-to-peak obviously weakens by force, and this has also illustrated in charging process, the Li in A1
2CO
3Decomposition has occured.Voltage platform in first all charging processes should react corresponding to this.
As a comparison, commercial Spinel LiMn2O4 (LiMn
2O
4) positive electrode first three all charging and discharging curve as shown in Figure 5.A1 was mixed by weight 1: 1 and is prepared into according to the method described above positive pole with this commercial manganate cathode material for lithium, and its first three all charging and discharging curve as shown in Figure 6.Both contrasts can find out, after adding A1, first all coulombic efficiencies of LiMn2O4 are reduced to 27.3% from 93.7%, produce a desired effect.
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Take 0.075mol ferric trichloride (FeCl
3) and 0.075mol lithium acetate (CH
3COOLi2H
2O), join in the container of the deionized water that contains 100 milliliters, be stirred to the solution clarification, then under strong agitation, dropwise splash into the aqueous solution that contains 0.150mol carbonic hydroammonium, then after fully stirring 24 hours, resulting solution is kept approximately 96h in the constant temperature oven of 50 ℃, to the complete evaporate to dryness of solution, obtain red gel shape material this moment.This red gel shape substance transfer to ball mill, is obtained dusty material after grinding about half an hour.This dusty material is placed in Muffle furnace, at 600 ℃ of roasting 10h, can obtains Fe of the present invention
3O
4-Li
2CO
3Nano composite material is designated as A2.
The primary particle of A2 is approximated to spherical, and average grain diameter is about 1～20nm, and numerous such primary particles are reunited and formed micron-sized second particle.Wherein the mol ratio of elemental lithium and ferro element is 1: 1.Be prepared into the positive pole of simulated battery by the method for embodiment 1, the specific capacity of its first all charging process reaches 354mAh/g, and first all specific discharge capacities are only 17mAh/g, referring to table 1.
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Take 0.025mol nickel sesquioxide (Ni in glove box
2O
3) and 0.05mol lithia (Li
2O), after fully grinding, transfer in the ball grinder of high energy ball mill, ball grinder is taken out after good seal in glove box, ball milling 10h shifts ball grinder into glove box again, takes out abrasive material, can obtain Ni of the present invention
2O
3-Li
2The O nano composite material is designated as A3.
The particle of A3 presents irregular shape, and the size of particle is greatly about the 100nm left and right.Wherein the mol ratio of elemental lithium and nickel element is 2: 1.In glove box with itself and carbon black and polytetrafluoroethylene (PTFE) mixed grinding and roll flakiness at normal temperatures and pressures, be cut into the approximately square sheets of 8 * 8mm, thin slice is placed on stainless (steel) wire, compress under 10MPa pressure, namely obtain the positive pole of simulated battery, its first all charge/discharge capacity sees Table 1.
Embodiment 4
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Take 0.025mol titanium dioxide (TiO
2) and 0.05mol lithium peroxide (Li
2O
2), after fully grinding in mortar, transferring in the ball grinder of high energy ball mill, then add the 20mL absolute ethyl alcohol, ball milling 6h takes out ball grinder, and the material in tank is taken out and namely obtain TiO of the present invention after 80 ℃ of oven dry
2-Li
2O
2Nano composite material is designated as A4.
The particle of A4 presents irregular shape, and the size of particle is greatly about the 100nm left and right.Wherein the mol ratio of elemental lithium and titanium elements is 4: 1.Be prepared into the positive pole of simulated battery by the method for embodiment 1, its first all charge/discharge capacity sees Table 1.
Embodiment 5～38
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Embodiment 5～38 is identical with the preparation method of embodiment 4, difference is, its raw material that adopt are different lithium salts or the oxide of lithium and oxides of different transition metal, what prepare is lithium salts or the oxide of lithium and the nano composite material of transition metal oxide with different primary particle sizes, is designated as respectively A5～A38.The chemical formula of the transition metal oxide in above-mentioned nano composite material can be written as M
aO
z, wherein, M is Ti, Cu, Mn, Fe, Co, Ni, Zn, Ag, Zr, Nb, Mo or W, a=0.5～3, z=0.5～5; The oxide of lithium salts or lithium can be lithium carbonate (Li
2CO
3), lithium peroxide (Li
2O
2), lithia (Li
2O), lithium oxalate (Li
2C
2O
4) and lithium acetate (CH
3COOLi) one or more in.The particle of resulting nano composite material presents irregular shape, and the size of particle is greatly about the 100nm left and right.Wherein, the mol ratio of elemental lithium and transition metal can be 0.25～8: 1.
The mol ratio of the concrete chemical composition of A5～A38, first all charge/discharge capacities and elemental lithium and transition metal sees Table the record in 1.
Embodiment 39～50
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Embodiment 39～50 is identical with the preparation method of embodiment 4, difference is, its raw material that adopt are different lithium salts or the oxide of lithium and different transition metal, what prepare is lithium salts or the oxide of lithium and the nano composite material of transition metal with different primary particle sizes, is designated as respectively A39～A50.Transition metal in above-mentioned nano composite material can be Ti, Cu, Mn, Fe, Co, Ni, Zn, Ag, Zr, Nb, one or more of Mo and W; The oxide of lithium salts or lithium can be lithium carbonate (Li
2CO
3), lithium peroxide (Li
2O
2), lithia (Li
2O), lithium oxalate (Li
2C
2O
4) and lithium acetate (CH
3COOLi) one or more in.The particle of resulting nano composite material presents irregular shape, and the size of particle is greatly about the 100nm left and right.Wherein, the mol ratio of elemental lithium and transition metal can be 0.25～8: 1.
The mol ratio of the concrete chemical composition of A39～A50, first all charge/discharge capacities and elemental lithium and transition metal sees Table the record in 2.
Embodiment 51
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Add the carbon black of 0.05g in the 0.85gA1, the water soluble starch of 0.1g, and the ethanol of 20mL, then high-energy ball milling 1 hour 24 hour carries out pyrolysis in 600 ℃ of lower sintering with mixture in argon gas, obtain the Ni-NiO-Li that carbon coats
2CO
3Nano composite material is designated as A51.Because after coating, NiO is converted to metal Ni substantially, so the actual sets of this compound becomes C-Ni-NiO-Li
2CO
3Ni-NiO-Li wherein
2CO
3The average grain diameter of the particle of nano composite material is 20～50nm, and percentage by weight is 88%, and the percentage by weight of carbon is 12%, and the thickness of carbon-coating is 20～30nm.A51 is prepared as positive pole, and its first all charge/discharge capacity sees Table 3.
Embodiment 52
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Carry out pyrolysis in 600 ℃ of heating 4h after A2 and ionic liquid [EMIm] [N (CN) 2] (1-ethyl-3-methy limidazoliumdicyanamide) are evenly mixed in argon gas atmosphere, obtain the Fe-Fe that carbon coats after cooling
3O
4-Li
2CO
3Nano composite material is designated as A52.Fe after coating
3O
4Substantially be converted to metal Fe, the actual sets of this nano composite material becomes C-Fe-Fe
3O
4-Li
2CO
3Fe-Fe wherein
3O
4-Li
2CO
3The average grain diameter of the particle of nano composite material is 1～20nm, and percentage by weight is 92%, and the percentage by weight of carbon is 8%, and the thickness of carbon-coating is about 10nm.A52 is prepared as positive pole, and its first all charge/discharge capacity sees Table 3.
Embodiment 53
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Get phenolic resins 1g, add in the 50mL absolute ethyl alcohol, be placed in 70 ℃ of constant temperature water baths, fully stir 1h, this moment, resin dissolved fully, slowly added afterwards the A5 of 0.1g, continued to stir until the ethanol distilled-to-dryness.The product that obtains is placed in tube furnace, and 1000 ℃ of sintering 2h carry out pyrolysis in argon gas, and products therefrom is the MnO-Li that carbon coats
2CO
3Nano composite material is designated as A53.After coating, MnO is converted to metal M n substantially, so the actual sets of this nano composite material becomes C-Mn-MnO-Li
2CO
3Wherein, Mn-MnO-Li
2CO
3The average grain diameter of the particle of nano composite material is about 100nm, and percentage by weight is 92.9%, and the percentage by weight of carbon is 7.1%, and the thickness of carbon-coating is about 6nm.A53 is prepared as positive pole, and its first all charge/discharge capacity sees Table 3.
Embodiment 54
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Take 0.025mol manganese acetate (Mn (CH
3COO)
24H
2O) and 0.05mol lithium acetate (CH
3COOLi2H
2O), join in the container of the deionized water that contains 100mL, be stirred to the solution clarification, then under strong agitation, dropwise splash into the aqueous solution that contains 0.1mol carbonic hydroammonium.In this process, solution becomes suspension-turbid liquid gradually by settled solution.After fully stirring 5h again, resulting suspension-turbid liquid was kept in the constant temperature oven of 100 ℃ approximately 1 hour, to the complete evaporate to dryness of suspension-turbid liquid, obtain green pasty masses this moment.Should be transferred in ball mill by the green pasty masses, obtain dusty material after grinding about half an hour.
This dusty material is placed in tube furnace, at 500 ℃ of lower roasting direct 5h, can obtains the Mn-MnO-Li that carbon coats
2CO
3Nano composite material is designated as A54.Mn-MnO-Li wherein
2CO
3The average grain diameter of the particle of nano composite material is about 100nm, and percentage by weight is 82%, and the percentage by weight of carbon is 18%, and the thickness of carbon-coating is about 50nm.A54 is prepared as positive pole, and its first all charge/discharge capacity sees Table 3.
Embodiment 55
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Get urea 3g, add in the 10mL absolute ethyl alcohol, fully stir 1h, this moment, urea dissolved fully, slowly added afterwards A6, continued to stir 1h.The suspension-turbid liquid that obtains is dried in the constant temperature oven of 80 ℃, grind and to obtain powder, be placed in tube furnace, 500 ℃ of sintering are 1 hour in argon gas atmosphere, and the product that obtains is the FeO-Li that carbon coats
2CO
3Nano composite material is designated as A55.Because after coating, FeO is converted to metal Fe substantially, so the actual sets of this nano composite material becomes C-Fe-FeO-Li
2CO
3Wherein, FeO-Li
2CO
3The particle of compound is about 100nm, and percentage by weight is 94%, and the percentage by weight of carbon is 6%, and the thickness of carbon-coating is about 1nm.A55 is prepared as positive pole, and its first all charge/discharge capacity sees Table 3.
Embodiment 56
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Ald (ALD) technology is by a kind of method that the pulse of gas phase presoma is alternately passed into reactor and then chemisorbed reacts the formation deposited film on depositing base.This method can make monoatomic layer successively deposit, and sedimentary deposit has thickness and excellent consistency extremely uniformly.
The present embodiment uses the ALD technology to prepare nickel oxide and lithium carbonate nano composite material that alundum (Al2O3) coats, and the presoma that uses is trimethyl aluminium (Al (CH
3)
3).
The preparation method is as follows: at first A1 and acetylene black, PVDF evenly are coated in above the Al paper tinsel of cleaning out in mass ratio at 80: 10: 10, thickness is 200 μ m approximately.Then system is vacuumized, when the reative cell vacuum reaches approximately 10
-2During torr, each parts of atomic layer deposition system are begun heating, wherein the temperature of reaction cavity is controlled at 250 ℃, and the temperature in trimethyl aluminium source is 150 ℃, and the temperature in aqueous vapor source is 150 ℃.When the probe temperature of system's each several part reaches target temperature, system is degassed, remove the steam in cavity; When the process of degassing complete with temperature stabilization after, pole piece is placed in the atomic layer deposition system reactor.Continue to be evacuated to the reative cell vacuum and reach 10
-1After torr, with H
2O and Al (CH
3)
3Precursor gas is with N
2For carrier gas is alternately sent in reactor, deposit 100 circulations, making electrode slice surface deposition thickness is the Al of 10nm
2O
3, namely make Al
2O
3The NiO-Li that coats
2CO
3Nano composite material is designated as A56.Take out sample after deposition finishes, cut into the electrode slice of 8 * 8mm size, 120 ℃ of dry 6h of vacuum, then the method according to embodiment 1 is assembled into simulated battery.This A56 is during as positive pole, and its first all charge/discharge capacity sees Table 4.
Embodiment 57～65
The present embodiment is used for preparation and the application of explanation nano composite material of the present invention.
Embodiment 57～65 is identical with the preparation method of embodiment 56, all adopts the ALD technology to carry out the surface to A1 and coats inert compound.Difference is that the presoma that adopts is different, and therefore resulting material is to have coated respectively TiO on the surface
2, ZrO
2, ZnO, HfO
2, SiO
2, MgO, AlPO
4, AlF
3Or ZrO
2NiO-Li
2CO
3Nano composite material is designated as respectively A57～A65.The thickness of above-mentioned inert compound layer is 1～10nm.Respectively when anodal, its first all charge/discharge capacity sees Table 4 with A57～A65.
Embodiment 66
The present embodiment is used for positive electrode and the serondary lithium battery of application nano composite material of the present invention.
With A1 and LiMn2O4 (LiMn
2O
4) mixed by weight 1: 4 after, and the n-formyl sarcolysine base pyrrolidone solution of acetylene black (AB) and Kynoar (PVDF) at normal temperatures and pressures the mixed-shaped form slurry (wherein wt is than being A1: LiMn
2O
4: AB: PVDF=16: 64: 10: 10), evenly be coated on aluminum substrates, then after 100 ℃ of vacuumize 5h, the film of gained compressed under 10MPa pressure, the film thickness of gained is 100 μ m approximately, are cut into the electrode slice of 8 * 8mm as the positive pole of simulated battery.Described A1 accounts for the 16wt% of anodal total weight.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is 1mol LiPF
6Be dissolved in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The electro-chemical test step of simulated battery:
At first charge to 4.5V with 10mA/g, then be discharged to 3.0V with 10mA/g.The first all discharge capacities of this battery are with LiMn
2O
4Weight calculate, still can reach 113mAh/g, with respect to commercial LiMn
2O
4Do not reduce.But for whole combination electrode, its first all coulombic efficiency is reduced to 64.1%, and is suitable with first all coulombic efficiencies of silicium cathode.This result shows that A1 is as LiMn
2O
4The functional additive of positive electrode can significantly reduce first all coulombic efficiencies of positive electrode.If as positive pole, as negative pole, have so the coulombic efficiency more than 90% with silicon in the first all charge and discharge cycles of this full battery system with above-mentioned positive electrode, also namely the irreversible capacity in first week is extremely low.
Embodiment 67
The present embodiment is used for positive electrode and the serondary lithium battery of application nano composite material of the present invention.
With A1 and cobalt acid lithium (LiCoO
2, diameter is 20 microns, bulk density is 3g/cm
3) and the n-formyl sarcolysine base pyrrolidone solution of acetylene black and Kynoar (PVDF) at normal temperatures and pressures the mixed-shaped form slurry (wherein wt is than being A1: LiCoO
2: AB: PVDF=12: 68: 10: 10), evenly be coated on aluminum substrates, then at 100 ℃ of lower vacuumize 5h, the film of gained compressed under 10MPa pressure, the film thickness of gained is 100 μ m approximately, are cut into the electrode slice of 8 * 8mm as the positive pole of simulated battery.Described A1 accounts for the 12wt% of anodal total weight.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is 1mol LiPF
6Be dissolved in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The electro-chemical test step of simulated battery:
At first charge to 4.5V with 10mA/g, then be discharged to 3.0V with 10mA/g.The first all discharge capacities of this battery are with LiCoO
2Weight calculate, can reach 137mAh/g, with respect to commercial LiCoO
2Do not reduce.But for whole combination electrode, its first all coulombic efficiency is reduced to 66.2%, and is suitable with first all coulombic efficiencies of silicium cathode.This result shows that A1 is as LiCoO
2The functional additive of positive electrode can significantly reduce first all coulombic efficiencies of positive electrode, if with above-mentioned positive electrode as positive pole, as negative pole, have so the coulombic efficiency more than 95% with silicon in the first all charge and discharge cycles of this full battery system, also namely the irreversible capacity in first week is extremely low.
Embodiment 68
The present embodiment is used for positive electrode and the serondary lithium battery of application nano composite material of the present invention.
With A1 and LiFePO4 (LiFePO
4) and the n-formyl sarcolysine base pyrrolidone solution of acetylene black and Kynoar (PVDF) at normal temperatures and pressures the mixed-shaped form slurry (wherein wt is than being A1: LiFePO
4: AB: PVDF=5: 75: 10: 10), evenly be coated on aluminum substrates, then at 100 ℃ of lower vacuumize 5h, the film of gained compressed under 10MPa pressure, the film thickness of gained is 100 μ m approximately, are cut into the electrode slice of 8 * 8mm as the positive pole of simulated battery.Described A1 accounts for the 5wt% of anodal total weight.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is 1mol LiPF
6Be dissolved in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The electro-chemical test step of simulated battery:
At first charge to 4.5V with 10mA/g, then be discharged to 3.0V with 10mA/g.The first all discharge capacities of this battery are with LiFePO
4Weight calculate, can reach 150mAh/g, with respect to commercial LiFePO
4Do not reduce.But for whole combination electrode, its first all coulombic efficiency is reduced to 71.4%, and is suitable with first all coulombic efficiencies of silicium cathode.This result shows that A1 is as LiFePO
4The functional additive of positive electrode can significantly reduce first all coulombic efficiencies of positive electrode, if with above-mentioned positive electrode as positive pole, as negative pole, have so the coulombic efficiency more than 95% with silicon in the first all charge and discharge cycles of this full battery system, also namely the irreversible capacity in first week is extremely low.
Embodiment 69
The present embodiment is used for positive electrode and the serondary lithium battery of application nano composite material of the present invention.
With A1 and lithium nickel cobalt manganese oxygen (LiNi
0.33Co
0.33Mn
0.33O
2, diameter is 8 μ m, bulk density is 2.6g/cm
3) and the n-formyl sarcolysine base pyrrolidone solution of acetylene black and Kynoar (PVDF) at normal temperatures and pressures the mixed-shaped form slurry (wherein wt is than being A1: LiNi
0.33Co
0.33Mn
0.33O
2: AB: PVDF=30: 50: 10: 10), evenly be coated on aluminum substrates, then at 100 ℃ of lower vacuumize 5h, the film of gained compressed under 10MPa pressure, the film thickness of gained is 100 μ m approximately, are cut into the electrode slice of 8 * 8mm as the positive pole of simulated battery.Described A1 accounts for the 30wt% of anodal total weight.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is 1mol LiPF
6Be dissolved in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The electro-chemical test step of simulated battery:
At first charge to 5V with 10mA/g, then be discharged to 3.5V with 10mA/g.The first all discharge capacities of this battery are with LiNi
0.33Mn
0.33Co
0.33O
2Weight calculate, can reach 150mAh/g, with respect to commercial LiNi
0.33Mn
0.33Co
0.33O
2Do not reduce.But for whole combination electrode, its first all coulombic efficiency is reduced to 60.0%, and is suitable with first all coulombic efficiencies of silicium cathode.This result shows that A1 is as LiNi
0.33Mn
0.33Co
0.33O
2The functional additive of positive electrode can significantly reduce first all coulombic efficiencies of positive electrode, if with above-mentioned positive electrode as positive pole, as negative pole, have so the coulombic efficiency more than 95% with silicon in the first all charge and discharge cycles of this full battery system, also namely the irreversible capacity in first week is extremely low.
The mol ratio of the chemical composition of the nano composite material of the oxide of table 1 transition metal oxide of the present invention and lithium salts and lithium, first all charging capacitys and elemental lithium and transition metal
The mol ratio of the chemical composition of the nano composite material of the oxide of table 2 transition metal of the present invention and lithium salts and lithium, first all charging capacitys and elemental lithium and transition metal
Chemical composition and first all charge/discharge capacities thereof of the nano composite material that table 3 carbon of the present invention coats
| Numbering | Chemical formula | First all charging capacitys (mAh/g) | First all discharge capacities (mAh/g) |
| A51 | Ni-NiO-Li 2CO 3 | 211 | 8 |
| A52 | Fe-Fe 3O 4-Li 2CO 3 | 326 | 17 |
| A53 | Mn-MnO-Li 2CO 3 | 344 | 12 |
| A54 | Mn-MnO-Li 2CO 3 | 334 | 12 |
| A55 | Fe-FeO-Li 2CO 3 | 362 | 10 |
Chemical composition and first all charge/discharge capacities thereof of the nano composite material that table 4 inert compound of the present invention coats
Although the present invention has carried out description to a certain degree, significantly, under the condition that does not break away from the spirit and scope of the present invention, can carry out the suitable variation of each condition.Be appreciated that to the invention is not restricted to described embodiment, and be attributed to the scope of claim, it comprises the replacement that is equal to of described each factor.
Claims (12)
1. nano composite material, described nano composite material comprises elemental lithium and transition metal, and wherein, described elemental lithium is from the oxide of lithium salts and/or lithium; Described transition metal is from the oxide of transition metal and/or transition metal; The mol ratio of described elemental lithium and transition metal is 0.25～8: 1, is preferably 1～4: 1.
2. nano composite material according to claim 1, wherein, the average grain diameter of the oxide of described lithium salts, lithium, transition metal and transition metal oxide is 1～100nm independently of one another, is preferably 1～50nm.
3. nano composite material according to claim 1 and 2, wherein, described lithium salts is one or more in lithium carbonate, lithium oxalate and lithium acetate, is preferably lithium carbonate; The oxide of described lithium is lithium peroxide or lithia; Described transition metal is Ti, Cu, Mn, Fe, Co, Ni, Zn, Ag, Zr, Nb, one or more in Mo and W; Described transition metal oxide is M
aO
z, wherein M is Ti, Cu, Mn, Fe, Co, Ni, Zn, Ag, Zr, Nb, Mo or W, a=0.5～3, z=0.5～5.
4. the described nano composite material of any one according to claim 1 to 3, wherein, the surface of described nano composite material is coated with carbon-coating and/or inert compound layer.
5. nano composite material according to claim 4, wherein, described carbon-coating is graphitized carbon or ungraphitised carbon; The thickness of described carbon-coating is 0.4～100nm, is preferably 1～10nm; Described inert compound is Al
2O
3, TiO
2, ZrO
2, ZnO, HfO
2, SiO
2, MgO, AlPO
4, AlF
3And ZrO
2In one or more; The thickness of described inert compound layer is 0.4～100nm, is preferably 1～10nm.
6. the described nano composite material of any one according to claim 1 to 5, wherein, described nano composite material be subsphaeroidal dusty material, filamentary material, club-shaped material, thin-film material or aperture be 1～100nm contain the hole material, be preferably subsphaeroidal dusty material.
7. the preparation method of the described nano composite material of claim 1 to 6 any one, described preparation method comprises chemical method or Physical;
Described chemical method comprises: preparation contains the mixed solution of lithium salts and transition metal salt, adds ammonium bicarbonate soln when stirring in mixed solution, and the mol ratio of described transition metal salt, lithium salts and carbonic hydroammonium is 1: 1～2: 2～4; After fully stirring under 50～100 ℃ standing 1～96 hour, after drying, products therefrom is ground, roasting, namely obtain nano composite material;
Described Physical comprises: the oxide of lithium salts and/or lithium is mixed with transition metal and/or transition metal oxide, fully grind and obtain nano composite material.
8. preparation method according to claim 7, wherein, in described chemical method, described lithium salts is lithium acetate, lithium oxalate, lithium chloride or lithium nitrate; Described transition metal salt is acetate, oxalates, chlorate or the nitrate of transition metal; The described well-beaten time is 1～24h; Described roasting condition is in 400～600 ℃ of roasting 1～10h under air atmosphere.
9. according to claim 7 or 8 described preparation methods, wherein, described preparation method also is included in the step of coated with carbon bed and/or the inert compound layer of described nano composite material.
10. serondary lithium battery positive electrode, wherein, the nano composite material that described positive electrode comprises the described nano composite material of any one in claim 1 to 6 or makes according to the described method of any one in claim 7 to 9.
11. positive electrode according to claim 10, wherein, described nano composite material accounts for 1～30wt% of positive electrode total weight, is preferably 5～16wt%; The positive active material of described positive electrode is selected from LiCoO
2, LiMn
2O
4, LiNi
1/3Co
1/3Mn
1/3O
2, LiFePO
4, xLi
2MnO
3(1-x) LiMO
2Or LiNi
0.5Mn
1.5O
4
12. serondary lithium battery, wherein, the positive pole of the described serondary lithium battery nano composite material or the described positive electrode of claim 10 or 11 that comprise the described nano composite material of any one in claim 1 to 6, make according to the described preparation method of any one in claim 7 to 9.
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| CN111029571A (en) * | 2019-11-22 | 2020-04-17 | 贵州唯特高新能源科技有限公司 | Preparation method of silicon dioxide uniformly doped iron phosphate |
| CN112018388A (en) * | 2019-05-31 | 2020-12-01 | 比亚迪股份有限公司 | Lithium ion battery anode additive and preparation method thereof, lithium ion battery anode and lithium ion battery |
| CN112216838A (en) * | 2019-07-11 | 2021-01-12 | 深圳市比亚迪锂电池有限公司 | Lithium ion battery positive electrode material, positive plate and lithium ion battery |
| CN113578222A (en) * | 2021-07-12 | 2021-11-02 | 浙江大学 | Nanocomposite synthesis device based on instantaneous high-temperature Joule heating method, preparation method and application |
| CN113839006A (en) * | 2020-06-24 | 2021-12-24 | 深圳市比亚迪锂电池有限公司 | Lithium ion battery anode slurry and lithium ion battery |
| CN113839007A (en) * | 2020-06-24 | 2021-12-24 | 深圳市比亚迪锂电池有限公司 | Lithium ion battery anode slurry and lithium ion battery |
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| CN106328899B (en) * | 2016-10-11 | 2019-06-21 | 苏州大学 | A kind of nano ternary positive electrode and preparation method thereof |
| CN107706351A (en) * | 2017-09-30 | 2018-02-16 | 深圳市贝特瑞纳米科技有限公司 | A kind of positive plate, preparation method and include its lithium ion battery |
| CN112018388A (en) * | 2019-05-31 | 2020-12-01 | 比亚迪股份有限公司 | Lithium ion battery anode additive and preparation method thereof, lithium ion battery anode and lithium ion battery |
| CN112216838A (en) * | 2019-07-11 | 2021-01-12 | 深圳市比亚迪锂电池有限公司 | Lithium ion battery positive electrode material, positive plate and lithium ion battery |
| CN112216838B (en) * | 2019-07-11 | 2022-07-22 | 深圳市比亚迪锂电池有限公司 | Lithium ion battery positive electrode material, positive plate and lithium ion battery |
| CN111029571A (en) * | 2019-11-22 | 2020-04-17 | 贵州唯特高新能源科技有限公司 | Preparation method of silicon dioxide uniformly doped iron phosphate |
| CN111029571B (en) * | 2019-11-22 | 2021-06-11 | 贵州唯特高新能源科技有限公司 | Preparation method of silicon dioxide uniformly doped iron phosphate |
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| CN113839006B (en) * | 2020-06-24 | 2023-07-11 | 深圳市比亚迪锂电池有限公司 | Lithium ion battery anode slurry and lithium ion battery |
| CN113578222A (en) * | 2021-07-12 | 2021-11-02 | 浙江大学 | Nanocomposite synthesis device based on instantaneous high-temperature Joule heating method, preparation method and application |
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