CN103137976B - Nano composite material and preparation method thereof and positive electrode and battery - Google Patents
Nano composite material and preparation method thereof and positive electrode and battery Download PDFInfo
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- CN103137976B CN103137976B CN201110380479.2A CN201110380479A CN103137976B CN 103137976 B CN103137976 B CN 103137976B CN 201110380479 A CN201110380479 A CN 201110380479A CN 103137976 B CN103137976 B CN 103137976B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a kind of 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.Present invention also offers the preparation method of described nano composite material, and comprise serondary lithium battery positive electrode and the serondary lithium battery of described nano composite material.
Description
Technical field
The present invention relates to a kind of nano composite material and its preparation method and application, relate to a kind of lithium-transition metal nano composite material and preparation method thereof particularly, and comprise serondary lithium battery positive electrode and the serondary lithium battery of described nano composite material.
Background technology
At present, commercial lithium-ion batteries generally adopts LiCoO
2positive pole, LiMn
2o
4positive pole, LiFePO
4positive pole and graphitized carbon negative material.There is certain irreversible capacity loss in graphitized carbon material, cause the head of this full battery system week coulombic efficiency only can reach about 92% in all charge and discharge cycles of head.In addition, because many limiting factors of graphitized carbon material negative pole are (as specific capacity is lower, high-rate charge-discharge capability is 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 intercalation potential is higher is the focus of current negative material research and development, comprise alloy type negative material, as material that is stanniferous, silicon; Transistion metal compound negative material, as the transistion metal compound containing Mn, Cr, Fe, Ni, Co; Containing the transistion metal compound material of lithium, as LiVO
2, LiTiO
2; Nontransition metal compound-material, as SnO
2, SnO, Sb
2o
3deng.But these high-capacity cathode material all exist a defect, in the de-lithium process namely after first all embedding lithiums, irreversible capacity is larger.Therefore, when applying this kind of material, the head of full battery system week coulombic efficiency can be caused to reduce further.
In order to solve the inefficient problem of negative pole initial charge/discharge, successively propose in prior art directly to add in lithium metal, negative pole in positive pole add lithium metal, positive pole adds to add containing the lithium of sealer, negative pole and adds compound containing lithium (as Li containing the lithium of sealer, negative pole
xtMN
y, TM=Co, Fe, Ni, Cu) or the method such as lithium alloy.But because these add material in atmosphere in unstable character, there is certain technical difficulty in actual applications, such as, in the processes such as electrode fabrication, battery assembling, there are a series of safety problems etc.
Summary of the invention
Therefore, the object of the invention is to overcome the inefficient defect of current negative pole initial charge/discharge, avoid the potential safety hazard caused because directly adding the materials such as lithium metal simultaneously, there is provided a kind of irreversible capacity that effectively can reduce or eliminate negative pole in the first all charge and discharge cycles of full battery system, to improve lithium-transition metal nano composite material of the first all coulombic efficiency of battery 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 from the oxide of lithium salts and/or lithium; Described transition metal can 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 one or more in Ti, Cu, Mn, Fe, Co, Ni, Zn, Ag, Zr, Nb, 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 containing Porous materials, be preferably subsphaeroidal dusty material.
Present invention also offers a kind of method preparing nano composite material of the present invention, 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, and in mixed solution, add ammonium bicarbonate soln when stirring, the mol ratio of described transition metal salt, lithium salts and carbonic hydroammonium is 1: 1 ~ 2: 2 ~ 4; At 50 ~ 100 DEG C, leave standstill 1 ~ 96 hour after abundant stirring, by products therefrom grinding, roasting after drying, namely obtain nano composite material;
Described Physical comprises: mixed with transition metal and/or transition metal oxide by the oxide of lithium salts and/or lithium, and fully grinding obtains 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 the acetate of transition metal, oxalates, chlorate or nitrate; The described well-beaten time can be 1 ~ 24h; Described roasting condition can be in air atmosphere in 400 ~ 600 DEG C of roasting 1 ~ 10h.
Preparation in accordance with the present invention, wherein, described preparation method is also included in the coated with carbon bed of described nano composite material and/or the step of inert compound layer.The method of described coated carbon-coating and/or inert compound can be:
Described nano composite material mixed with the precursor of carbon, pyrolysis in inert atmosphere or reducing atmosphere at 300 ~ 1000 DEG C, makes its coated with carbon bed; And/or
Described nano composite material is adopted chemical vapour deposition technique, makes organic gas pyrolysis in inert atmosphere or reducing atmosphere at 300 ~ 1000 DEG C, make its coated with carbon bed; And/or
Described nano composite material is put into ionic liquid or form slurry like material containing organic solution, 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, makes its Surface coating inert compound layer.
Invention further provides a kind of serondary lithium battery positive electrode, 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.
Present invention also offers a kind of serondary lithium battery, 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 may be used for all kinds of mobile electronic device or fixed power-supply device, the fields such as 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 be obtained by very easy method, and raw material and manufacturing cost are all lower, are easy to large-scale production.
(2) nano composite material provided by the invention is when the first week charging of battery, charging capacity can reach 100 ~ 400mAh/g, and discharge capacity is less than 10mAh/g, therefore the additive of positive electrode is suitable as very much, in circulation in first week, irreversibly provide excessive lithium ion, compensate the irreversible capacity of lithium cell cathode material.
(3) nano composite material of the present invention, compared with lithium metal, the adding material such as lithium metal, lithium alloys through protecting, stable chemical nature, security performance is high, is convenient to storage and uses.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 a and Fig. 1 b shows 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;
Fig. 4 shows X ray diffracting spectrum when nickel oxide and lithium carbonate nano composite material prepared by the embodiment of the present invention 1 and head thereof charge to 4.5V, 4.8V week; Wherein, curve 1), curve 2) and curve 3) represent respectively described nano composite material before charging, charge to 4.5V, collection of illustrative plates when charging to 4.8V;
Fig. 5 shows first three week charging and discharging curve of commercial Spinel lithium manganese oxygen positive electrode;
Fig. 6 shows nickel oxide and lithium carbonate nano composite material prepared by the embodiment of the present invention 1 and commercial Spinel lithium manganese oxygen positive electrode 1: 1 first three week charging and discharging curve mixing the positive electrode prepared afterwards by weight.
Embodiment
Further illustrate the present invention below by specific embodiment, but should be understood to, these embodiments are only used for the use specifically described more in detail, and should not be construed as limiting the present invention in any form.
General description is carried out to the material used in the present invention's test and test method in this part.Although for realizing many materials that the object of the invention uses and method of operation is well known in the art, the present invention still describes in detail as far as possible at this.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and method of operation are well known in the art.
embodiment 1
The present embodiment is for illustration of the preparations and applicatio of nano composite material of the present invention.
Take 0.025mol nickel acetate (Ni (CH
3cOO)
24H
2and 0.05mol lithium acetate (CH O)
3cOOLi2H
2o), join in the container containing the deionized water of 100 milliliters, be stirred to solution clarification, then under vigorous stirring, the dropwise aqueous solution of instillation containing 0.075mol carbonic hydroammonium.In the process, solution becomes green suspension-turbid liquid gradually by green settled solution.Fully stir after 1 hour again, obtained green suspension-turbid liquid is kept about 72h in the constant temperature oven of 80 DEG C, to the complete evaporate to dryness of green suspension-turbid liquid, now obtain green gel shape material.
By this green gel shape substance transfer in ball mill, grind and about obtain dusty material after half an hour.This dusty material is placed in Muffle furnace, 400 DEG C of roastings 1 hour, NiO-Li of the present invention can be obtained
2cO
3nano composite material, is denoted as A1.
Field emission scanning electron microscope (S-4800, Hitachi, Ltd, the Japan of product A 1, accelerating voltage 10 kilovolts) photo is as shown in Figure 1, the primary particle of visible product is approximated to spherical, and average grain diameter is about 20 ~ 50nm, and numerous such primary particle is reunited and constituted micron-sized second particle.As shown in Figure 2, the main component of visible product is Li to the X ray diffracting spectrum (X ' PertProMPD, PHILIPS Co., Holland) of A1
2cO
3, NiO and W metal.In analysis of chemical elements result display product A 1, the mol ratio of elemental lithium and nickel element is 2: 1.
The nitrogen methylpyrrolidone solution of A1 and acetylene black (AB) and 10% Kynoar (PVDF) is mixed to form slurry at normal temperatures and pressures, and (weight ratio is A1: acetylene black: PVDF=80: 10: 10), even application is in aluminum substrates, then dry 5h at 60 DEG C, the film of gained is tight at 10MPa pressure, be then cut into the positive pole of electrode slice as simulated battery of 8 × 8mm.
The negative pole of simulated battery uses lithium sheet, and electrolyte is 1molLiPF
6be dissolved in (solvent volume ratio is 1: 1) in the mixed solvent of 1LEC (ethylene carbonate) and DMC (dimethyl carbonate).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:
First charge to 4.5V with 10mA/g, then be discharged to 2.0V with 10mA/g, then repeat this two processes successively, its charging and discharging capacity to the curve of voltage as shown in Figure 3.Can find out, 240mAh/g (see table 1) can be reached by the specific capacity of the positive pole prepared by A1 in initial charge process, and the specific capacity in discharge process is first only 8mAh/g.Therefore its irreversible capacity is very high, can irreversibly provide excessive lithium ion, compensate the negative pole lithium ion that irreversible reaction consumes in first Zhou Xunhuan in circulation in first week.
Positive pole prepared by A1 is charged to the X ray diffracting spectrum after 4.5V and 4.8V 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, this also illustrates in charging process, the Li in A1
2cO
3there occurs decomposition.Voltage platform in first all charging processes should correspond to this reaction.
As a comparison, commercial Spinel LiMn2O4 (LiMn
2o
4) positive electrode first three week charging and discharging curve as shown in Figure 5.Mixed with this commercial manganate cathode material for lithium by weight 1: 1 and be prepared into positive pole according to the method described above by A1, the charging and discharging curve in its first three week as shown in Figure 6.Both can find out in contrast, and after adding A1, the head week coulombic efficiency of LiMn2O4 is reduced to 27.3% from 93.7%, produces a desired effect.
embodiment 2
The present embodiment is for illustration of the preparations and applicatio of 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 containing the deionized water of 100 milliliters, be stirred to solution clarification, then under vigorous stirring, the dropwise aqueous solution of instillation containing 0.150mol carbonic hydroammonium, more fully stir after 24 hours, obtained solution is kept about 96h in the constant temperature oven of 50 DEG C, to the complete evaporate to dryness of solution, now obtain red gel shape material.By this red gel shape substance transfer in ball mill, grind and about obtain dusty material after half an hour.This dusty material is placed in Muffle furnace, at 600 DEG C of roasting 10h, Fe of the present invention can be obtained
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 particle is reunited and constituted 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, see table 1.
embodiment 3
The present embodiment is for illustration of the preparations and applicatio of nano composite material of the present invention.
0.025mol nickel sesquioxide (Ni is taken in glove box
2o
3) and 0.05mol lithia (Li
2o), fully after 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, again ball grinder is shifted into glove box, take out abrasive material, Ni of the present invention can be obtained
2o
3-Li
2o nano composite material, is designated as A3.
The particle of A3 presents irregular shape, and the size of particle is greatly about about 100nm.Wherein the mol ratio of elemental lithium and nickel element is 2: 1.By itself and carbon black and polytetrafluoroethylene (PTFE) mixed grinding roll flakiness at normal temperatures and pressures in glove box, be cut into the square sheets of about 8 × 8mm, thin slice is placed on stainless (steel) wire, tight at 10MPa pressure, namely obtain the positive pole of simulated battery, its first all charge/discharge capacity is in table 1.
embodiment 4
The present embodiment is for illustration of the preparations and applicatio of 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, transfer in the ball grinder of high energy ball mill, then add 20mL absolute ethyl alcohol, ball milling 6h, take out ball grinder, the material in tank is taken out and namely obtain TiO of the present invention after 80 DEG C 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 about 100nm.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 is in table 1.
embodiment 5 ~ 38
The present embodiment is for illustration of the preparations and applicatio of nano composite material of the present invention.
Embodiment 5 ~ 38 is identical with the preparation method of embodiment 4, difference is, its raw material adopted are the oxide of different lithium salts or lithium and the oxide of different transition metal, what prepare is the nano composite material with the different lithium salts of primary particle size or the oxide of lithium and transition metal oxide, is designated as A5 ~ A38 respectively.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 the nano composite material obtained presents irregular shape, and the size of particle is greatly about about 100nm.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, in the record in table 1.
embodiment 39 ~ 50
The present embodiment is for illustration of the preparations and applicatio of nano composite material of the present invention.
Embodiment 39 ~ 50 is identical with the preparation method of embodiment 4, difference is, its raw material adopted are the oxide of different lithium salts or lithium and different transition metal, what prepare is the nano composite material with the different lithium salts of primary particle size or the oxide of lithium and transition metal, is designated as A39 ~ A50 respectively.Transition metal in above-mentioned nano composite material can be one or more of Ti, Cu, Mn, Fe, Co, Ni, Zn, Ag, Zr, Nb, 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 the nano composite material obtained presents irregular shape, and the size of particle is greatly about about 100nm.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, in the record in table 2.
embodiment 51
The present embodiment is for illustration of the preparations and applicatio of nano composite material of the present invention.
The carbon black of 0.05g is added, the water soluble starch of 0.1g in 0.85gA1, and the ethanol of 20mL, high-energy ball milling 1 hour, then sinters mixture and carries out pyrolysis in 24 hours, obtain the Ni-NiO-Li that carbon is coated in argon gas at 600 DEG C
2cO
3nano composite material, is designated as A51.Because coated rear NiO is converted to W metal substantially, the actual sets of this compound becomes C-Ni-NiO-Li
2cO
3.Wherein Ni-NiO-Li
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 is in table 3.
embodiment 52
The present embodiment is for illustration of the preparations and applicatio of nano composite material of the present invention.
Carrying out pyrolysis by heating 4h in 600 DEG C after A2 and ionic liquid [EMIm] [N (CN) 2] (1-ethyl-3-methylimidazoliumdicyanamide) Homogeneous phase mixing in argon gas atmosphere, after cooling, obtaining the Fe-Fe that carbon is coated
3o
4-Li
2cO
3nano composite material, is designated as A52.Coated rear Fe
3o
4substantially be converted to metal Fe, the actual sets of this nano composite material becomes C-Fe-Fe
3o
4-Li
2cO
3.Wherein Fe-Fe
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 is in table 3.
embodiment 53
The present embodiment is for illustration of the preparations and applicatio of nano composite material of the present invention.
Get phenolic resins 1g, add in 50mL absolute ethyl alcohol, be placed in 70 DEG C of constant temperature water baths, fully stir 1h, now resin dissolves completely, slowly adds the A5 of 0.1g afterwards, continues to stir until ethanol distilled-to-dryness.The product obtained is placed in tube furnace, and in argon gas, 1000 DEG C of sintering 2h carry out pyrolysis, and products therefrom is the coated MnO-Li of carbon
2cO
3nano composite material, is designated as A53.Coated rear MnO is converted to metal M n substantially, so the actual sets of this nano composite material becomes C-Mn-MnO-Li
2cO
3.Wherein, 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 is in table 3.
embodiment 54
The present embodiment is for illustration of the preparations and applicatio of nano composite material of the present invention.
Take 0.025mol manganese acetate (Mn (CH
3cOO)
24H
2and 0.05mol lithium acetate (CH O)
3cOOLi2H
2o), join in the container of the deionized water containing 100mL, be stirred to solution clarification, then under vigorous stirring, the dropwise aqueous solution of instillation containing 0.1mol carbonic hydroammonium.In the process, solution becomes suspension-turbid liquid gradually by settled solution.After fully stirring 5h again, obtained suspension-turbid liquid is kept about 1 hour in the constant temperature oven of 100 DEG C, to the complete evaporate to dryness of suspension-turbid liquid, now obtains green pasty masses.This green pasty masses is transferred in ball mill, grinds and about obtain dusty material after half an hour.
This dusty material is placed in tube furnace, roasting direct 5h at 500 DEG C, the Mn-MnO-Li that carbon is coated can be obtained
2cO
3nano composite material, is designated as A54.Wherein Mn-MnO-Li
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 is in table 3.
embodiment 55
The present embodiment is for illustration of the preparations and applicatio of nano composite material of the present invention.
Get urea 3g, add in 10mL absolute ethyl alcohol, fully stir 1h, now urea dissolves completely, slowly adds A6 afterwards, continues to stir 1h.Dried in the constant temperature oven of 80 DEG C by the suspension-turbid liquid obtained, grinding obtains powder, is placed in tube furnace, and in argon gas atmosphere, 500 DEG C sinter 1 hour, and the product obtained is the coated FeO-Li of carbon
2cO
3nano composite material, is designated as A55.Because coated rear FeO is converted to metal Fe substantially, the actual sets of this nano composite material becomes C-Fe-FeO-Li
2cO
3.Wherein, 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 is in table 3.
embodiment 56
The present embodiment is for illustration of the preparations and applicatio of nano composite material of the present invention.
Ald (ALD) technology is by vaporous precursors pulse alternately being passed into reactor and then chemisorbed is reacted and formed a kind of method of deposited film on depositing base.This method can make monoatomic layer successively deposit, and sedimentary deposit has extremely uniform thickness and excellent consistency.
The present embodiment uses ALD technology to prepare the coated nickel oxide of alundum (Al2O3) and lithium carbonate nano composite material, and the presoma of use is trimethyl aluminium (Al (CH
3)
3).
Preparation method is as follows: first by A1 and acetylene black, PVDF in mass ratio 80: 10: 10 even application on the Al paper tinsel cleaned out, thickness about 200 μm.Then system is vacuumized, when reative cell vacuum reaches about 10
-2start heating to each parts of atomic layer deposition system during torr, wherein the temperature of reaction cavity controls at 250 DEG C, and the temperature in trimethyl aluminium source is 150 DEG C, and the temperature in aqueous vapor source is 150 DEG C.When the probe temperature of system components reaches target temperature, system is degassed, the steam in removing cavity; When the process of degassing complete with temperature stabilization after, pole piece is placed in atomic layer deposition system reactor.Continue to be evacuated to reative cell vacuum and reach 10
-1after torr, by H
2o and Al (CH
3)
3precursor gas is with N
2for carrier gas is alternately sent in reactor, deposit 100 circulations, make electrode slice surface deposition thickness be the Al of 10nm
2o
3, i.e. obtained Al
2o
3coated NiO-Li
2cO
3nano composite material, is designated as A56.Deposition terminates rear taking-up sample, and cut into the electrode slice of 8 × 8mm size, vacuum 120 DEG C of dry 6h, are then assembled into simulated battery according to the method for embodiment 1.When this A56 is as positive pole, its first all charge/discharge capacity is in table 4.
embodiment 57 ~ 65
The present embodiment is for illustration of the preparations and applicatio of nano composite material of the present invention.
Embodiment 57 ~ 65 is identical with the preparation method of embodiment 56, all adopts ALD technology to carry out Surface coating inert compound to A1.Difference is that the presoma adopted is different, and therefore obtained material is coated respectively TiO on surface
2, ZrO
2, ZnO, HfO
2, SiO
2, MgO, AlPO
4, AlF
3or ZrO
2niO-Li
2cO
3nano composite material, is designated as A57 ~ A65 respectively.The thickness of above-mentioned inert compound layer is 1 ~ 10nm.During using A57 ~ A65 as positive pole, its first all charge/discharge capacity is in table 4.
embodiment 66
The present embodiment is for illustration of positive electrode and the serondary lithium battery of applying nano composite material of the present invention.
By A1 and LiMn2O4 (LiMn
2o
4) after 1: 4 mixing, and the nitrogen methylpyrrolidone solution of acetylene black (AB) and Kynoar (PVDF) is mixed to form slurry at normal temperatures and pressures, and (wherein weight ratio is A1: LiMn
2o
4: AB: PVDF=16: 64: 10: 10), even application is in aluminum substrates, then after 100 DEG C of vacuumize 5h, the film of gained is tight at 10MPa pressure, the film thickness of gained about 100 μm, is cut into the positive pole of electrode slice as simulated battery of 8 × 8mm.Described A1 accounts for the 16wt% of positive pole total weight.
The negative pole of simulated battery uses lithium sheet, and electrolyte is 1molLiPF
6be dissolved in (volume ratio 1: 1) in the mixed solvent of 1LEC and DMC.By 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:
First charge to 4.5V with 10mA/g, be then discharged to 3.0V with 10mA/g.The first all discharge capacities of this battery are with LiMn
2o
4weight computation, still can reach 113mAh/g, relative to commercial LiMn
2o
4do not reduce.But for whole combination electrode, its first all coulombic efficiency is reduced to 64.1%, suitable with the head week coulombic efficiency of silicium cathode.This result shows that A1 is as LiMn
2o
4the functional additive of positive electrode significantly can reduce the head week coulombic efficiency of positive electrode.If using above-mentioned positive electrode as positive pole, using silicon as negative pole, so have the coulombic efficiency of more than 90% 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 67
The present embodiment is for illustration of positive electrode and the serondary lithium battery of applying nano composite material of the present invention.
By A1 and cobalt acid lithium (LiCoO
2, diameter is 20 microns, and bulk density is 3g/cm
3) and the nitrogen methylpyrrolidone solution of acetylene black and Kynoar (PVDF) is mixed to form slurry at normal temperatures and pressures, and (wherein weight ratio is A1: LiCoO
2: AB: PVDF=12: 68: 10: 10), even application is in aluminum substrates, and then vacuumize 5h at 100 DEG C, tight at 10MPa pressure by the film of gained, the film thickness of gained about 100 μm, is cut into the positive pole of electrode slice as simulated battery of 8 × 8mm.Described A1 accounts for the 12wt% of positive pole total weight.
The negative pole of simulated battery uses lithium sheet, and electrolyte is 1molLiPF
6be dissolved in (volume ratio 1: 1) in the mixed solvent of 1LEC and DMC.By 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:
First charge to 4.5V with 10mA/g, be then discharged to 3.0V with 10mA/g.The first all discharge capacities of this battery are with LiCoO
2weight computation, can 137mAh/g be reached, relative to commercial LiCoO
2do not reduce.But for whole combination electrode, its first all coulombic efficiency is reduced to 66.2%, suitable with the head week coulombic efficiency of silicium cathode.This result shows that A1 is as LiCoO
2the functional additive of positive electrode significantly can reduce the head week coulombic efficiency of positive electrode, if using above-mentioned positive electrode as positive pole, using silicon as negative pole, so have the coulombic efficiency of more than 95% 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 for illustration of positive electrode and the serondary lithium battery of applying nano composite material of the present invention.
By A1 and LiFePO4 (LiFePO
4) and the nitrogen methylpyrrolidone solution of acetylene black and Kynoar (PVDF) is mixed to form slurry at normal temperatures and pressures, and (wherein weight ratio is A1: LiFePO
4: AB: PVDF=5: 75: 10: 10), even application is in aluminum substrates, and then vacuumize 5h at 100 DEG C, tight at 10MPa pressure by the film of gained, the film thickness of gained about 100 μm, is cut into the positive pole of electrode slice as simulated battery of 8 × 8mm.Described A1 accounts for the 5wt% of positive pole total weight.
The negative pole of simulated battery uses lithium sheet, and electrolyte is 1molLiPF
6be dissolved in (volume ratio 1: 1) in the mixed solvent of 1LEC and DMC.By 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:
First charge to 4.5V with 10mA/g, be then discharged to 3.0V with 10mA/g.The first all discharge capacities of this battery are with LiFePO
4weight computation, can 150mAh/g be reached, relative to commercial LiFePO
4do not reduce.But for whole combination electrode, its first all coulombic efficiency is reduced to 71.4%, suitable with the head week coulombic efficiency of silicium cathode.This result shows that A1 is as LiFePO
4the functional additive of positive electrode significantly can reduce the head week coulombic efficiency of positive electrode, if using above-mentioned positive electrode as positive pole, using silicon as negative pole, so have the coulombic efficiency of more than 95% 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 for illustration of positive electrode and the serondary lithium battery of applying nano composite material of the present invention.
By A1 and lithium nickel cobalt manganese oxygen (LiNi
0.33co
0.33mn
0.33o
2, diameter is 8 μm, and bulk density is 2.6g/cm
3) and the nitrogen methylpyrrolidone solution of acetylene black and Kynoar (PVDF) is mixed to form slurry at normal temperatures and pressures, and (wherein weight ratio is A1: LiNi
0.33co
0.33mn
0.33o
2: AB: PVDF=30: 50: 10: 10), even application is in aluminum substrates, and then vacuumize 5h at 100 DEG C, tight at 10MPa pressure by the film of gained, the film thickness of gained about 100 μm, is cut into the positive pole of electrode slice as simulated battery of 8 × 8mm.Described A1 accounts for the 30wt% of positive pole total weight.
The negative pole of simulated battery uses lithium sheet, and electrolyte is 1molLiPF
6be dissolved in (volume ratio 1: 1) in the mixed solvent of 1LEC and DMC.By 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:
First charge to 5V with 10mA/g, be then 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 computation, can 150mAh/g be reached, relative 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%, suitable with the head week coulombic efficiency of silicium cathode.This result shows that A1 is as LiNi
0.33mn
0.33co
0.33o
2the functional additive of positive electrode significantly can reduce the head week coulombic efficiency of positive electrode, if using above-mentioned positive electrode as positive pole, using silicon as negative pole, so have the coulombic efficiency of more than 95% 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
The chemical composition of the nano composite material that table 3 carbon of the present invention is coated and first all charge/discharge capacities thereof
| 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 |
The chemical composition of the nano composite material that table 4 inert compound of the present invention is coated and first all charge/discharge capacities thereof
Although present invention has been description to a certain degree, significantly, under the condition not departing from the spirit and scope of the present invention, can carry out the suitable change of each condition.Be appreciated that and the invention is not restricted to described embodiment, and be attributed to the scope of claim, it comprises the equivalent replacement of described each factor.
Claims (17)
1. a serondary lithium battery positive electrode, wherein, described positive electrode comprises nano composite material, and 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;
Described nano composite material accounts for 1 ~ 30wt% of positive electrode total weight; 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
4or LiNi
0.5mn
1.5o
4.
2. positive electrode according to claim 1, wherein, described nano composite material accounts for 5 ~ 16wt% of positive electrode total weight.
3. positive electrode according to claim 1, wherein, the mol ratio of described elemental lithium and transition metal is 1 ~ 4:1.
4. positive electrode 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.
5. positive electrode 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 ~ 50nm independently of one another.
6. positive electrode according to claim 1, wherein, described lithium salts is one or more in lithium carbonate, lithium oxalate and lithium acetate; The oxide of described lithium is lithium peroxide or lithia; Described transition metal is one or more in Ti, Cu, Mn, Fe, Co, Ni, Zn, Ag, Zr, Nb, 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.
7. positive electrode according to claim 1, wherein, described lithium salts is lithium carbonate.
8. positive electrode according to any one of claim 1 to 7, wherein, the Surface coating of described nano composite material has carbon-coating and/or inert compound layer.
9. positive electrode according to claim 8, wherein, described carbon-coating is graphitized carbon or ungraphitised carbon; The thickness of described carbon-coating is 0.4 ~ 100nm; 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.
10. positive electrode according to claim 8, wherein, the thickness of described carbon-coating is 1 ~ 10nm.
11. positive electrodes according to claim 8, wherein, the thickness of described inert compound layer is 1 ~ 10nm.
12. positive electrodes according to any one of claim 1 to 7, wherein, described nano composite material to be subsphaeroidal dusty material, filamentary material, club-shaped material, thin-film material or aperture be 1 ~ 100nm containing Porous materials.
13. positive electrodes according to any one of claim 1 to 7, wherein, described nano composite material is subsphaeroidal dusty material.
14. for the preparation of the method for the positive electrode according to any one of claim 1 to 13, and wherein, the method comprises the step preparing described nano composite material, and it comprises chemical method or Physical;
Described chemical method comprises: preparation contains the mixed solution of lithium salts and transition metal salt, and in mixed solution, add ammonium bicarbonate soln when stirring, the mol ratio of described transition metal salt, lithium salts and carbonic hydroammonium is 1:1 ~ 2:2 ~ 4; At 50 ~ 100 DEG C, leave standstill 1 ~ 96 hour after abundant stirring, by products therefrom grinding, roasting after drying, namely obtain nano composite material;
Described Physical comprises: mixed with transition metal and/or transition metal oxide by the oxide of lithium salts and/or lithium, and fully grinding obtains nano composite material.
15. methods according to claim 14, wherein, in described chemical method, described lithium salts is lithium acetate, lithium oxalate, lithium chloride or lithium nitrate; Described transition metal salt is the acetate of transition metal, oxalates, chlorate or nitrate; The described well-beaten time is 1 ~ 24h; Described roasting condition is in air atmosphere in 400 ~ 600 DEG C of roasting 1 ~ 10h.
16. preparation methods according to claims 14 or 15, wherein, described preparation method is also included in the coated with carbon bed of described nano composite material and/or the step of inert compound layer.
17. 1 kinds of serondary lithium batteries, wherein, the positive pole of described serondary lithium battery comprises the positive electrode according to any one of claim 1 to 13.
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| 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 |
| CN112018388B (en) * | 2019-05-31 | 2021-12-07 | 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 |
| 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 |
| 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 |
| 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 |
| CN113839007B (en) * | 2020-06-24 | 2023-07-07 | 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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| CN1416189A (en) * | 2001-11-02 | 2003-05-07 | 中国科学院物理研究所 | Lithium secondary battery by use of composite material covered with nano surface as active material of positive polar |
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| CN1416189A (en) * | 2001-11-02 | 2003-05-07 | 中国科学院物理研究所 | Lithium secondary battery by use of composite material covered with nano surface as active material of positive polar |
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