CN102227021A - Preparation method for anode composite materials of lithium ion batteries - Google Patents
Preparation method for anode composite materials of lithium ion batteries Download PDFInfo
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- CN102227021A CN102227021A CN201110131075XA CN201110131075A CN102227021A CN 102227021 A CN102227021 A CN 102227021A CN 201110131075X A CN201110131075X A CN 201110131075XA CN 201110131075 A CN201110131075 A CN 201110131075A CN 102227021 A CN102227021 A CN 102227021A
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- composite material
- metal salt
- anode composite
- divalent metal
- lithium ion
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a method for preparing anode composite materials of lithium ion batteries by reacting a stripped graphite oxide colloidal solution with LiOH, H3PO4, divalent metal salt and Vc to obtain anode composite materials of lithium batteries. And the metal ions in the divalent metal salt are Fe<2+>, Co<2+>, Ni<2+> and Mn<2+>. Compared with the prior art, the method of the invention, used for preparing LiMPO4/graphene composite materials, has the advantages of simplicity, low temperature, no need for atmosphere protection, low cost, low energy consumption and the like. And the obtained composite materials of lithium batteries can charge and discharge directly without adding any conductive agent.
Description
Technical field
The present invention relates to composite material, be specifically related to a kind of preparation method of anode composite material of lithium ion battery
Background technology
Lithium ion battery is a kind of novel high-performance battery that grows up on the basis of lithium battery, because its function admirable, since its commercialization, be widely used in mancarried electronic aids such as mobile phone, notebook computer, video camera, and replaced nickel-hydrogen, nickel-pneumatic cell gradually in this field.In addition, increasingly serious along with problems such as energy-conservation and environmental protection, electric vehicle with the battery by the energy is accepted by people widely, and the lithium ion battery that therefore is applied in fields such as electric automobile, large-sized power power supply has huge market and potential advantages.
Anode material for lithium-ion batteries surface discharge process is: when battery discharge, the lithium ion that is in the hole enters the Li that makes the positive active material in the pore from hole wall
+Embed in the active material, simultaneously the Li in the pore
+Concentration reduces.Polarization increases if electric current strengthens, and the discharge difficulty is accompanied by battery discharge, Li
+Embed in the active material, also must inject electronics.Olivine-type LiFePO
4As anode material for lithium-ion batteries have that raw material is cheap, aboundresources, big capacity, extra long life, safe in utilization, high temperature resistant, the incomparable advantages of other lithium ion batteries such as storge quality is good, environmental protection, can be widely used in electric bicycle and hybrid vehicle, have very wide application prospect.
But, LiFePO
4Battery material also has some defectives: at first, be subjected to the restriction of electronics of material own and ionic conductivity, be difficult to directly as positive electrode, so in the prior art generally at LiFePO
4Doping C or use C coat LiFePO
4Material is mixed C and can further be reduced tap density, because its solid density only is 3.6g/cm
3(cobalt acid lithium 5.1g/cm
3), the tap density of general carbon dope LiFePO4 is about 1.0g/cm
3For LiFePO
4The composite material that this class carbon of/C coats, at present the source of the C that coats just have multiple, the Vc of sucrose, glucose, ascorbic acid high temperature cabonization for example, multilayer carbon nanotube and acetylene black etc.
Graphene (Graphene) is the two-dimentional carbon atom crystal of monatomic thickness, and (thickness only is for the present the thinnest material that manually makes
), it is believed that it is the basic structural unit of fullerene, carbon nano-tube and graphite.The theoretical specific area of Graphene and derivative thereof is up to 2630m
2/ g has outstanding heat conductivility (3000Wm
-1) and mechanical property (1000GPa), and higher electron mobility (15000cm under the room temperature
2V
-1S
-1), can be used for energy storage, nanoelectronic element, nano-machines and Composite Preparation.Therefore, can be with Graphene as clad material, for improvement LiFePO
4The shortcoming of electronic conductivity difference own will play important effect.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of method for preparing the lithium battery anode composite material, and compared with prior art, the lithium battery anode composite material of method preparation provided by the invention has better charge-discharge performance.
In order to solve above technical problem, the invention provides a kind of preparation method of lithium battery anode composite material, comprising:
Make colloidal solution and LiOH, the H of the graphite oxide of peeling off
3PO
4, divalent metal salt, Vc carry out the reactive lithium battery anode composite material, the metal ion in the described divalent metal salt is Fe
2+, Co
2+, Ni
2+, Mn
2+
Preferably, described method is specially:
A) provide the colloidal solution of the graphite oxide of peeling off;
B) make described colloidal solution and LiOH, H
3PO
4, divalent metal salt, Vc carry out the reactive lithium battery anode composite material, the metal ion in the described divalent metal salt is Fe
2+, Co
2+, Ni
2+, Mn
2+In one or more.
Preferably, described divalent metal salt is MSO
4, described M is one or more among Fe, Co, Ni or the Mn.
Preferably, the colloidal solution in the described step b) and described LiOH, H
3PO
4, divalent metal salt and the mixed mixed liquor of Vc the pH value be 6～7.
Preferably, in the described step b) Li: the mol ratio of M: P is 2～4: 0.5～1.5: 0.5～1.5.
Preferably, the reaction temperature in the described step b) is at least 150 ℃.
Preferably, the reaction time of described step c) is 5h at least.
Preferably, the step that also comprises washing and dry described product.
The present invention also provides a kind of anode composite material of lithium ion battery according to method for preparing.
The present invention also provides a kind of lithium ion battery active anode compartment, is made by described anode composite material of lithium ion battery
The invention provides a kind of method for preparing anode composite material of lithium ion battery, comprising: the colloidal solution and LiOH, the H that make the graphite oxide of peeling off
3PO
4, divalent metal salt, Vc carry out the reactive lithium battery anode composite material, the metal ion in the described divalent metal salt is Fe
2+, Co
2+, Ni
2+, Mn
2+Compared with prior art, the composite material of method preparation of the present invention uses Graphene to coat LiMPO
4, experimental result shows that the composite material of the present invention's preparation has better charge-discharge performance.That the method for preparing the lithium battery anode composite material provided by the invention has is easy, low temperature, need not advantages such as atmosphere protection, the cost of raw material is low, power consumption is low, and the lithium battery anode composite material that obtains can directly discharge and recharge, and need not to add conductive agent.
Description of drawings
Fig. 1 is the XRD diffracting spectrum of the composite material of the embodiment of the invention 1 preparation;
Fig. 2 is a lithium ion battery structure schematic diagram provided by the invention.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The invention provides a kind of method for preparing anode composite material of lithium ion battery, comprising:
Make colloidal solution and LiOH, the H of the graphite oxide of peeling off
3PO
4, divalent metal salt, Vc carry out the reactive lithium battery anode composite material, the metal ion in the described divalent metal salt is Fe
2+, Co
2+, Ni
2+, Mn
2+Reaction temperature is preferably at least 150 ℃, and more preferably at least 160 ℃, more preferably at least 180 ℃.
According to the present invention, described method preferably includes:
A) provide the colloidal solution of the graphite oxide of peeling off;
B) make described colloidal solution and LiOH, H
3PO
4, divalent metal salt, Vc carry out the reactive lithium battery anode composite material, the metal ion in the described divalent metal salt is Fe
2+, Co
2+, Ni
2+, Mn
2+In one or more.
According to the present invention, the colloidal solution of the described graphite oxide of peeling off preferably makes with the following method preparation: add graphite oxide in the deionized water or LiOH solution in, the colloidal solution of the graphite oxide that ultrasonic Treatment can obtain peeling off.The time of sonicated is preferably 15min at least, 20min at least more preferably, more preferably 30min at least.After the sonicated, magnetic agitation is spent the night, and obtains the brown graphite oxide colloidal solution of peeling off.
According to the present invention, the LiOH concentration in the described colloidal solution is preferably 0.1mol/L～0.5mol/L, more preferably 0.15mol/L～0.45mol/L, more preferably 0.2mol/L～0.4mol/L, more preferably 0.25mol/L～0.35mol/L.The LiOH in the described colloidal solution and the weight ratio of graphite oxide are preferably 4～8: 1, more preferably 5～7: 1, and more preferably 6: 1.
According to the present invention, when using colloidal solution to prepare anode composite material of lithium ion battery, add LiOH, H
3PO
4, divalent metal salt, Vc react and obtain anode composite material of lithium ion battery.For the addition sequence of several raw materials, the present invention is also without particular limitation.Metal ion in the described divalent metal salt is Fe
2+, Co
2+, Ni
2+, Mn
2+In one or more.The object lesson of divalent metal salt can be FeSO
4, CoSO
4, NiSO
4, MnSO
4In one or more, but be not limited thereto.
According to the present invention, the preferred LiOH that adds earlier adds H then
3PO
4And FeSO
4, add Vc at last.Specifically as follows:
Under the stirring, add LiOH solution in described graphite oxide colloidal solution, the concentration of LiOH solution is preferably 0.1mol/L～0.5mol/L, more preferably 0.15mol/L～0.45mol/L, more preferably 0.2mol/L～0.4mol/L, more preferably 0.25mol/L～0.35mol/L.Then, under protective atmosphere, in described colloidal solution, add H
3PO
4/ FeSO
4, control Li: Fe: P is 2～4: 0.5～1.5 according to mol ratio: 0.5～1.5, more preferably 2.5～3.5: 0.5～1.5: 0.5～1.5, more preferably 3: 0.8～1.1: 0.8～1.1, and more preferably 3: 1: 1.
Add H
3PO
4/ FeSO
4After obtaining mixed liquor, can add the pH value that Vc regulates colloidal solution is 6～7, more preferably 6.1～6.9, more preferably 6.3～6.7.Then, mixed liquor is put into baking oven reacting more than 150 ℃, preferred reaction temperature is more than 155 ℃, more preferably more than 165 ℃, more preferably more than 170 ℃.Reaction time is preferably at least 5 hours, and more preferably at least 6 hours, more preferably at least 7 hours.
After the reaction,, filter drying with the atrament washing that reaction obtains.Described baking temperature is preferably at least 100 ℃, and more preferably at least 105 ℃, more preferably at least 110 ℃, more preferably at least 115 ℃; Described drying is preferably carried out under vacuum condition.
Below with specific embodiment effect of the present invention is described, but protection scope of the present invention is not limited by the following examples.
Embodiment 1:
Be the raw material that sets out with graphite powder, adopt improved Hummer method (Xiaojing Yang, Yoji Makita, Zong-huai Liu, Kenta Ooi, Chem.Mater.2003,15,1228-1231) oxidation, preparation graphite oxide (GO).Getting 1g GO adding 160ml concentration is that magnetic agitation is spent the night behind the ultrasonic 30min in the LiOH solution of 0.3mol/L, obtains the brown GO colloid of peeling off.Get 5mL GO stripper, stirring and at N
2Protection adds the LiOH solution of 20mL 0.3mol/L earlier down, adds 25mL 0.1mol/L H then
3PO
4/ FeSO
4Solution, keep Li: Fe: the P mol ratio is 3: 1: 1, adds 0.44g Vc, regulating the pH value at last is 6.6.Need in the whole process to stir, front gained solution is put into water heating kettle, then water heating kettle is put into baking oven, 170 ℃ of insulation 6h.With the atrament washing that obtains, filter 110 ℃ of vacuumizes.
The product that obtains is carried out XRD test, test condition: Cu target (K
α, λ=0.15406nm), Ni filtering, voltage is 36KV, electric current is 20mA: 4.5 °～70 ° of sweep limitss (2 θ), sweep speed is 2 °/min, the result shows to have generated LiFePO shown in the curve a of Fig. 1
4
Behind the product removal LiFePO 4 that obtains, measured X RD, curve show to have generated Graphene as shown in curve b in Figure 1.
Embodiment 2
Get the freeze-dried GO of 0.0625g, add the 25mL deionized water, obtain the GO colloidal solution that pale brown look is peeled off behind the ultrasonic 30min.Stirring and at N
2Protection adds 0.695g FeSO down
47H
2O and 0.44g Vc then add 0.3147g LiOHH
2O adds 25mL 0.1mol/L H subsequently
3PO
4Solution, keep Li: Fe: the P mol ratio is 3: 1: 1, and regulating pH at last is 6.5.The mixed liquor that obtains is put into water heating kettle, then water heating kettle is put into baking oven, temperature insulation 6h more than 170 ℃.With the atrament washing that obtains, filter 110 ℃ of vacuumizes.
Embodiment 3
Method according to embodiment 1 prepares the GO colloidal solution of peeling off.Get 10mL GO colloidal solution, stirring and at N
2Protection adds the LiOH solution of 15mL 0.3mol/L earlier down, adds 0.695g FeSO again
47H
2O and 1.32g Vc add 25mL0.1mol/L H then
3PO
4Solution, keep Li: Fe: the P mol ratio is 3: 1: 1, regulates pH value to 6.7.The mixed liquor that obtains is put into water heating kettle, then water heating kettle is put into baking oven, 170 ℃ of insulation 6h reaction.With the atrament washing that obtains after the reaction, to filter, 110 ℃ of vacuumizes obtain the black product.
Embodiment 4
Method according to embodiment 2 makes the GO colloidal solution of peeling off.Get 15mL GO stripper, stirring N
2Protection adds 15mL 0.3mol/L LiOH solution down, adds 0.695g FeSO again
47H
2O and 25mL 0.1mol/L H
3PO
4Solution adds 1.32gVc at last, and keeping Li: Fe: P is 3: 1: 1, and regulating the pH value at last is 6.8.The aforementioned solution that obtains is put into water heating kettle, then water heating kettle is put into baking oven, temperature insulation 6h more than 170 ℃ with the atrament washing that obtains, filters, and 110 ℃ of vacuumizes obtain the black product.
Embodiment 5
Method according to embodiment 1 makes the GO colloidal solution of peeling off.Get 15mL GO stripper, stirring N
2Protection adds 0.695g FeSO down
47H
2O and 1.32g Vc, the LiOH solution of adding 15mL 0.3mol/L adds 25mL 0.1mol/L H again
3PO
4Solution, keeping Li: Fe: P is 3: 1: 1, regulating the pH value at last is 6.8.The aforementioned solution that obtains is put into water heating kettle, then water heating kettle is put into baking oven, temperature insulation 6h more than 170 ℃ with the atrament washing that obtains, filters, and 110 ℃ of vacuumizes obtain the black product.
Embodiment 6
Method according to embodiment 1 makes the GO colloidal solution of peeling off.Get 15mL GO stripper, stirring N
2Protection adds the LiOH solution of 15mL 0.3mol/L down, adds 0.695g FeSO
47H
2O and 1.32g Vc add 25mL 0.1mol/LH at last
3PO
4Solution, keeping Li: Fe: P is 3: 1: 1, regulating the pH value at last is 6.8.The aforementioned solution that obtains is put into water heating kettle, then water heating kettle is put into baking oven, temperature insulation 6h more than 170 ℃ with the atrament washing that obtains, filters, and 110 ℃ of vacuumizes obtain the black product.
Embodiment 7
Method according to embodiment 1 makes the GO colloidal solution of peeling off.Get 15mL GO stripper, stirring N
2Protection adds 0.695g FeSO down
47H
2O and 1.32g Vc add 25mL 0.1mol/L H
3PO
4Solution adds the LiOH solution of 15mL 0.3mol/L at last, and keeping Li: Fe: P is 3: 1: 1, and regulating the pH value at last is 6.7.The aforementioned solution that obtains is put into water heating kettle, then water heating kettle is put into baking oven, temperature insulation 6h more than 170 ℃ with the atrament washing that obtains, filters, and 110 ℃ of vacuumizes obtain the black product.
Embodiment 8
Get that the composite material acid of embodiment 1～5 preparation is molten (uses HCl/HNO
3/ H
2Each 1/3 volume of O) behind the removal LiFePO 4 Graphene and the raw material GO that obtains carried out elementary analysis, the result is as shown in table 1:
The elementary analysis wt% of the Graphene in the composite material of table 1 the present invention preparation
From the result of table 1 as can be seen, obtained Graphene in the complex of embodiment of the invention 1-5 preparation, compared with the GO that adds before the reaction, though also have some oxygen-containing functional groups that do not react completely, oxygen content is whole descend a lot.
Embodiment 9 preparation active anode compartment films
90: 10 ratio weighing with the anode composite material of lithium ion battery of embodiment 1 preparation according to the mass ratio of composite material: PVDF;
Anode composite material is placed the mortar porphyrize, place beaker.In beaker, use liquid-transfering gun dropwise to add the PVDF solvent in the mixture according to aforementioned proportion.The solidliquid mixture that stirs fast in the beaker is extremely thick, places under the infrared lamp to take off behind baking 10min～15min.Biased sample is poured over through alcohol swab being positioned on the aluminium foil surface on the clean glass plate of wiping repeatedly, use the slow thick material that will mix at the uniform velocity of coating machine to push into film, after putting under the infrared lamp baking drying, be transferred to dried overnight in 110 ℃ of vacuum drying chambers.
The installation of embodiment 102032-button cell
The diameter of the lithium ion button shape cell of 2032 expression assemblings is 20mm, and thickness is 3.2mm.As shown in Figure 2, using hydraulic press to be pressed into the uniform cathode film of thickness the above-mentioned cathode film that is applied on the aluminium foil, is negative pole with the metal lithium sheet, and concentration of electrolyte is 1mol/L, LiPF
6(EC: DMC: the EMC mass ratio is 1: 1: 1) mixed solution, in order: the order of negative electrode casing-lithium sheet-barrier film-electrolyte-positive plate-steel disc-shell fragment-anode cover is assembled simulated battery in inert atmosphere glove box (Mikrouna Supen 1220/750), (CT2001A) carries out charge-discharge test with the LAND battery test system, charging and discharging currents density is more than the 0.1C, the charging/discharging voltage scope is 2.0V～4.3V, and 100 capacity that circulate are undamped substantially.
More than the preparation method of lithium battery anode composite material provided by the invention is described in detail.Used specific case herein principle of the present invention and execution mode are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of claim of the present invention.
Claims (10)
1. method for preparing anode composite material of lithium ion battery comprises:
Make colloidal solution and LiOH, the H of the graphite oxide of peeling off
3PO
4, divalent metal salt, Vc carry out the reactive lithium battery anode composite material, the metal ion in the described divalent metal salt is Fe
2+, Co
2+, Ni
2+, Mn
2+
2. method according to claim 1 is characterized in that, described method is specially:
A) provide the colloidal solution of the graphite oxide of peeling off;
B) make described colloidal solution and LiOH, H
3PO
4, divalent metal salt, Vc carry out the reactive lithium battery anode composite material, the metal ion in the described divalent metal salt is Fe
2+, Co
2+, Ni
2+, Mn
2+In one or more.
3. method according to claim 2 is characterized in that, described divalent metal salt is MSO
4, described M is one or more among Fe, Co, Ni or the Mn.
4. according to claim 2 or 3 described methods, it is characterized in that the colloidal solution in the described step b) and described LiOH, H
3PO
4, divalent metal salt and the mixed mixed liquor of Vc the pH value be 6～7.
5. method according to claim 4 is characterized in that, in the described step b) Li: the mol ratio of M: P is 2～4: 0.5～1.5: 0.5～1.5.
6. method according to claim 4 is characterized in that, the reaction temperature in the described step b) is at least 150 ℃
7. method according to claim 4 is characterized in that, the reaction time of described step c) is 5h at least.
8. according to right 5 described methods, it is characterized in that, also comprise the step of washing and dry described product.
9. according to the anode composite material of lithium ion battery of each described method preparation of claim 1 to 8.
10. a lithium ion battery active anode compartment is characterized in that, is made by the described anode composite material of lithium ion battery of claim 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105826524A (en) * | 2016-03-18 | 2016-08-03 | 山东科技大学 | Synthesis method of lithium iron phosphate of graphene in-situ nucleation |
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Application publication date: 20111026 |