CN103165883B - Lithium ion battery phosphate anode composite material and its production and use - Google Patents
Lithium ion battery phosphate anode composite material and its production and use Download PDFInfo
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- CN103165883B CN103165883B CN201110425631.4A CN201110425631A CN103165883B CN 103165883 B CN103165883 B CN 103165883B CN 201110425631 A CN201110425631 A CN 201110425631A CN 103165883 B CN103165883 B CN 103165883B
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Abstract
The present invention relates to lithium ion battery phosphate anode composite material and its production and use.Particularly, the invention discloses a kind of phosphate anode composite material of lithium ion battery and there is LiMn
1-xfe
xpO
4and Li
3v
2(PO
4)
3two kinds of lattice structures, chemical formula is yLiMn
1-xfe
xpO
4(1-y) Li
3v
2(PO
4)
3/ C, wherein x=0.00-0.40, y=0.50-0.95, C are carbon-coating.And disclose the Preparation method and use of described composite material.Composite material of the present invention has high potential platform 4.1V, high reversible capacity, good circulation stability, and electricity warning function is with low cost, the advantages such as environmental protection.
Description
Technical field
The invention belongs to electrode material field, be specifically related to field of lithium ion battery, particularly a kind of lithium ion battery phosphate anode composite material and its production and use.
Background technology
Lithium ion battery is a kind of very outstanding battery system.Along with the continuous progress of science and technology, people are more and more strong to the demand of the removable energy, and continually developing of new forms of energy is the important foundation of human kind sustainable development.Lithium ion battery since commercialization at the beginning of the eighties in last century, because of its have that voltage is high, specific energy is high, have extended cycle life, the feature such as non-environmental-pollution, be widely used in the portable electric appts such as mobile phone, notebook computer, miniature camera.The non-renewable resources such as traditional oil, natural gas can also be replaced; obtain extensive use more in fields such as electric tool, electric bicycle, electric automobile, solar cell and wind energy battery energy storage, satellite and space flight, thus play an important role in protection of the environment, the saving irreproducibility energy etc.
Occur till now from lithium ion battery, positive electrode mainly contains compound and the modified composites thereof such as cobalt acid lithium, lithium nickelate, lithium nickel cobalt dioxide, cobalt nickel lithium manganate ternary material, nickel cobalt lithium aluminate ternary material, LiMn2O4, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium.
But the current the most successful application of lithium ion battery is still in the portable electric appts such as mobile phone, notebook computer, miniature camera, digital product, and wherein most anode material for lithium-ion batteries is all cobalt acid lithium, existing market occupation rate still reaches more than 80%.Because cobalt has the shortcoming such as resource scarcity and toxicity, lithium cobaltate cathode material cost is more and more higher, increasing to environmental impact, and the fail safe of cobalt acid lithium is poor, can not be applied to electrokinetic cell field.
Other positive electrode of lithium ion battery, as the researchs such as lithium nickelate, lithium nickel cobalt dioxide, cobalt nickel lithium manganate ternary material, nickel cobalt lithium aluminate ternary material, LiMn2O4, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium have made great progress, lithium nickelate, lithium nickel cobalt dioxide, cobalt nickel lithium manganate ternary material, nickel cobalt lithium aluminate material, LiMn2O4, LiFePO4 etc. just launch application in market.
But lithium nickelate, lithium nickel cobalt dioxide, cobalt nickel lithium manganate ternary material, nickel cobalt lithium aluminate material all belong to lamellar structure, lattice structure is unstable, and easily produce oxygen, fail safe is poor, and cost is higher, has a strong impact on pragmatize application; LiMn2O4 reversible capacity is lower, and actual only have about 110mAh/g, and volume and capacity ratio is lower, and the manganese ion in lattice easily dissolves more than 55 DEG C, and cause crystal structure to destroy, cyclical stability is poor, and cycle life is poor; LiFePO4 cyclical stability is fine, and fail safe is good, and reversible capacity is higher, but its voltage platform is lower, and tap density is lower, causes volume and weight specific capacity lower, and very smooth voltage platform makes the monitoring of the electricity of its battery more difficult.
Therefore, this area is in the urgent need to studying a kind of new substitution material.
Summary of the invention
The object of the invention is, provide a kind of phosphate anode composite material of lithium ion battery and preparation method thereof, and composite material does positive electrode thus, graphite or lithium titanate material do the lithium rechargeable battery that negative material forms.
First aspect present invention provides a kind of phosphate anode composite material of lithium ion battery, and described composite material comprises crystal grain and is coated on the carbon-coating outside crystal grain, and wherein said crystal grain has following lattice structure: LiMn
1-xfe
xpO
4lattice structure and Li
3v
2(PO
4)
3lattice structure, in formula, x=0.00-0.40.
In another preference, described LiMn
1-xfe
xpO
4lattice structure is olivine structural, and described Li
3v
2(PO
4)
3for NASICON structure is determined.
In another preference, the chemical formula of described composite material is yLiMn
1-xfe
xpO
4(1-y) Li
3v
2(PO
4)
3/ C, wherein, x=0.00-0.40, y=0.50-0.95, described C is carbon-coating.
In another preference, y=0.55-0.90, preferably, y=0.60-0.80;
In another preference, x=0.05-0.35, preferably, x=0.10-0.20;
In another preference, described LiMn
1-xfe
xpO
4or Li
3v
2(PO
4)
3particle diameter be 10nm-5000nm.
In another preference, described LiMn
1-xfe
xpO
4or Li
3v
2(PO
4)
3particle diameter be 10nm-500nm.
Second aspect present invention provides a kind of anode, and described positive pole contains the anode composite material described in first aspect present invention.
In another preference, described positive pole is also containing conductive agent and binding agent.
In another preference, described conductive agent is acetylene black;
In another preference, described binding agent is Kynoar;
Third aspect present invention provides a kind of lithium rechargeable battery, and described battery contains the anode described in second aspect present invention.
Fourth aspect present invention provides a kind of lithium rechargeable battery, described lithium rechargeable battery comprises positive electrode, negative material, barrier film, electrolyte and shell, wherein, described positive electrode comprises the phosphate anode composite material of lithium ion battery described in first aspect present invention.
In another preference, described negative material comprises native graphite, electrographite, carbonaceous mesophase spherules, carborundum, metal lithium sheet or lithium titanate.
In another preference, described barrier film is PP & PE barrier film or fibreglass diaphragm.
Fifth aspect present invention provides a kind of preparation method of anode composite material as described in the first aspect of the invention, comprises step:
A () is by lithium source material, manganese source material, ferrous source material, vanadium source material, phosphate radical source material, carbon source material, be 1.10-2.00: 0.30-0.95: 0.00-0.38: 0.10-1.00: 1.10-2.00: 1.57-2.61 mixing by lithium, manganese, iron, vanadium, phosphorus, carbon molar ratio, add dispersant, by ball mill process, thus form the presoma through ball milling;
In another preference, described dispersant is absolute ethyl alcohol or ethylene glycol.
In another preference, the time of described ball mill process is 1-10 hour.
The b presoma through ball milling that step (a) obtains by () by heat treated, thus is formed through heat treated mixture;
C mixture cooling that step (b) obtains by (), thus form the anode composite material described in first aspect present invention.
In another preference, also comprise step between step (b) and step (c): step (b) obtain after the cooling of heat treated mixture, mix with carbon source material, and by ball mill process, obtain the mixture through ball milling, wherein, the addition of described carbon source material is the 5%-20% of the weight of carbon source material in step (a).
In another preference, described step (b) comprises step:
(b-1) precursor that step (a) obtains is placed in tube furnace in 300-500 DEG C of heat treatment 3-20h, cools rear thus formed through 1 heat treated mixture;
(b-2) mixture that step (b-1) obtains is placed in tube furnace heat treatment 4-36h under 500-900C, thus is formed through 2 heat treated mixtures.
In another preference, between described step (b-1) and step (b-2), also comprise step: mixture step (b-1) obtained is through ball-milling treatment.
Sixth aspect present invention provides the preparation method of the anode composite material described in a kind of first aspect present invention, comprises step:
A () provides LiMn
1-xfe
xpO
4/ C and Li
3v
2(PO
4)
3/ C, wherein, x=0.00-0.40, described C are carbon-coating;
B () is according to y: the LiMn of molar ratio ball milling blend step (a) of (1-y)
1-xfe
xpO
4/ C and Li
3v
2(PO
4)
3/ C, wherein, x=0.00-0.40, y=0.50-0.95, thus form the anode composite material described in first aspect present invention.
In another preference, step (b) is by the LiMn of step (a)
1-xfe
xpO
4/ C and Li
3v
2(PO
4)
3/ C, wherein, x=0.00-0.40, y=0.50-0.95, according to y: after the molar ratio ball milling mixing of (1-y), carry out heat treated, thus form the anode composite material described in first aspect present invention.
In another preference, described heat treated is process at 200-300 DEG C.
In another preference, described ball milling mixing apparatus is high energy ball mill or planetary ball mill.
In another preference, described LiMn
1-xfe
xpO
4/ C, wherein, x=0.00-0.40, its preparation comprises the following steps:
I () is by lithium source material, manganese source material, ferrous source material, phosphate radical source material, carbon source material, be 1.00: 0.60-0.95: 0-0.40: 1.00: 1.50-3.30 mixing by lithium, manganese, iron, phosphorus, carbon molar ratio, add dispersant, by ball mill process, obtain the presoma through ball milling;
In another preference, described dispersant is absolute ethyl alcohol or ethylene glycol.
In another preference, the time of described ball mill process is 1-10 hour.
(i-1) presoma that step (i) obtains is placed in tube furnace 300-500 DEG C of heat treatment 3-20h, obtains through 1 heat treated mixture after cooling;
(i-2) mixture that step (i-1) obtains is placed in tube furnace heat treatment 4-36h at 500-900 DEG C, obtains through 2 heat treated mixtures;
(ii) mixture cooling step (ii-2) obtained, obtained LiMn
1-xfe
xpO
4/ C, wherein, x=0.00-0.40.
In another preference, also comprise step between step (i-2) and step (ii): step (i-2) obtain after the cooling of heat treated mixture, mix with carbon source material, and by ball mill process, obtain the mixture through ball milling, wherein, the addition of described carbon source material is the 5%-20% of the weight of carbon source material in step (i).
In another preference, described Li
3v
2(PO
4)
3the preparation of/C comprises the following steps:
A lithium source material, vanadium source material, phosphate radical source material, carbon source material are 3.00: 2.00: 3.00: 3.80-8.50 be placed in high energy ball mill by lithium, vanadium, phosphorus, carbon molar ratio by (), add dispersant, ball milling 2-10 hour obtained precursor;
B described precursor is placed in argon hydrogen gaseous mixture tube furnace 300-500 DEG C of heat treatment 3-15h by (), take out ball milling 2-10b;
C () is placed in argon hydrogen gaseous mixture tube furnace 500-900 DEG C of heat treatment 3-36h again, obtained Li
3v
2(PO
4)
3/ C.
Seventh aspect present invention provides the purposes of the composite material described in a kind of first aspect present invention, for the preparation of lithium rechargeable battery.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Figure 1A is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 1.
Figure 1B is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 1.
Fig. 1 C is the distribution diagram of element of composite material prepared by embodiment 1.
Fig. 1 D is the x-ray diffraction pattern of composite material prepared by embodiment 1.
Fig. 1 E is composite material discharge capacity cycle graph prepared by embodiment 1.
Fig. 2 A is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 2.
Fig. 2 B is the x-ray diffraction pattern of composite material prepared by embodiment 2.
Fig. 3 A is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 3.
Fig. 3 B is the x-ray diffraction pattern of composite material prepared by embodiment 3.
Fig. 4 A is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 4a.
Fig. 4 B is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 4b.
Fig. 4 C is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 4.
Fig. 4 D is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 4.
Fig. 4 E is the distribution diagram of element of composite material prepared by embodiment 4.
Fig. 4 F is the x-ray diffraction pattern of embodiment 4a, 4b, 4 composite materials prepared.
Fig. 4 G is the composite material discharge capacity cycle graph of embodiment 4a, 4b, 4 preparations.
Fig. 5 A is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 5a.
Fig. 5 B is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 5b.
Fig. 5 C is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 5.
Fig. 5 D is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 5.
Fig. 5 E is the distribution diagram of element of composite material prepared by embodiment 5.
Fig. 5 F is the x-ray diffraction pattern of embodiment 5a, 5b, 5 composite materials prepared.
Fig. 5 G is the composite material discharge capacity cycle graph of embodiment 5a, 5b, 5 preparations.
Fig. 6 A is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 6a.
Fig. 6 B is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 6b.
Fig. 6 C is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 6.
Fig. 6 D is the x-ray diffraction pattern of embodiment 6a, 6b, 6 composite materials prepared.
Fig. 7 A is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 7.
Fig. 7 B is the scanning electron microscope (SEM) photograph of composite material prepared by embodiment 7.
Fig. 7 C is the distribution diagram of element of composite material prepared by embodiment 7.
Fig. 7 D is composite material x-ray diffraction pattern prepared by embodiment 7.
Fig. 7 E is composite material discharge capacity cycle graph prepared by embodiment 7.
Fig. 8 is the first charge-discharge curve of embodiment 4a, 6a, 7 composite materials prepared.
Fig. 9 is the composite material prepared of embodiment 7 and the full battery first charge-discharge Capacity Plan assembled of lithium titanate.
Embodiment
Present inventor is through extensively and in depth studying, unexpected discovery, by adopting iron ion to the Some substitute of manganese ion, its conductivity is improved under the prerequisite not affecting lithium manganese phosphate reversible capacity, by the compound with phosphoric acid vanadium lithium, improve the cyclical stability of phosphoric acid vanadium lithium, reduce material cost, obtained phosphate anode composite material of lithium ion battery (yLiMn
1-xfe
xpO
4(1-y) Li
3v
2(PO
4)
3/ C, wherein x=0.00-0.40, y=0.50-0.95) possessed the advantage of lithium manganese phosphate and phosphoric acid vanadium lithium simultaneously, there is high potential platform, high reversible capacity, good circulation stability, electricity warning function, with low cost, the advantages such as environmental protection.On this basis, the present invention is completed.
Lithium manganese phosphate (LiMnPO
4)
Lithium manganese phosphate (LiMnPO
4) Stability Analysis of Structures, there is high potential (platform voltage 4.1V).The olivine structural LiMnPO of pure phase
4for insulator, conductivity is very low, does not have practical use, therefore by nanometer or element doping, the modified method such as alternative, coated, must improve its conductivity, improve its high rate performance, cycle performance and reversible capacity.
Phosphoric acid vanadium lithium (Li
3v
2(PO
4)
3)
Phosphoric acid vanadium lithium (Li
3v
2(PO
4)
3) there is high potential, high conductivity.Pure phase Li
3v
2(PO
4)
3cost is higher, and its 4.6V voltage platform cannot practical application under current electrolysis liquid system, causes its actual reversible capacity to only have about 130mAh/g, and therefore application difficult is larger separately.
Phosphate anode composite material of lithium ion battery
Phosphate lithium ion anode composite material provided by the invention, described composite material comprises crystal grain and is coated on the carbon-coating outside crystal grain, and wherein said crystal grain has following lattice structure: LiMn
1-xfe
xpO
4lattice structure and Li
3v
2(PO
4)
3lattice structure, in formula, x=0.00-0.40.
Wherein, described LiMn
1-xfe
xpO
4lattice structure is olivine structural, and described Li
3v
2(PO
4)
3for NASICON structure.
Described coated can be all coated or part is coated.
The chemical formula of described composite material is yLiMn
1-xfe
xpO
4(1-y) Li
3v
2(PO
4)
3/ C, wherein, x=0.00-0.40, y=0.50-0.95, described C is carbon-coating.
Preferably, y=0.55-0.90, preferably, y=0.60-0.80;
Preferably, x=0.05-0.35, preferably, x=0.10-0.20;
Composite material of the present invention also can not mix iron (when x is 0), and described composite material possesses lithium manganese phosphate and phosphoric acid vanadium lithium advantage simultaneously.
And the present invention is by adopting iron ion to the Some substitute (when x is not 0) of manganese ion, under the prerequisite not affecting lithium manganese phosphate reversible capacity, improves its conductivity, and do not affect its reversible capacity.Due to Li
3v
2(PO
4)
3platform is had, respectively with LiMnPO at 4.1V and 3.6V
4(4.1V) and LiFePO
4(3.4V) platform is close, and conductivity is higher, therefore, the lithium manganese phosphate of iron ion doping and phosphoric acid vanadium lithium composite material also can possess lithium manganese phosphate and phosphoric acid vanadium lithium advantage simultaneously, as high potential platform 4.1V, high reversible capacity 150mAh/g, cyclical stability, with low cost, environmental protection etc., and both shortcomings can be improved by doping iron ion, make composite material of the present invention be more suitable for practical application.
The preparation of phosphate anode composite material of lithium ion battery
In preparation method of the present invention, required lithium source material, manganese source material, ferrous source material, vanadium source material, phosphate radical source material, carbon source material and equipment all can be bought in market and obtain.The experimental technique of unreceipted actual conditions, the usually conveniently conditioned disjunction condition of advising according to manufacturer.Such as precursor treatment facility is: high energy ball mill, stainless cylinder of steel and stainless steel ball; In argon hydrogen gaseous mixture, hydrogen content is 0-10%, and impurity content is less than 0.01%; Ball milling, adopt planetary ball mill, stainless steel ball and tank, bulb diameter is 10mm, dry mill process etc.
LiMn of the present invention
1-xfe
xpO
4and Li
3v
2(PO
4)
3the complex method of crystal grain be heat chemistry compound (as in 300-500 DEG C of heat treatment 3-20h or at 500-900 DEG C heat treatment 4-36h), after room temperature physics compound (as ball milling mixing) or room temperature physical mixed heat chemistry (after ball milling mixing, carry out heat treated) compound, be preferably heat chemistry compound.
Described lithium source material is: lithium dihydrogen phosphate, lithium carbonate, lithium hydroxide, lithium fluoride, lithium nitrate, lithium phosphate, the one in lithium acetate or its combination;
Described manganese source material is: manganese carbonate, manganese acetate, manganese dioxide, the one in manganese phosphate or its combination;
Described ferrous source material is: iron oxide, iron powder, ferric nitrate, ferric phosphate, the one in ferric oxalate or its combination;
Described vanadium source material is: vanadic oxide, the one in ammonium metavanadate or its combination;
Described phosphate radical source material is: ammonium dihydrogen phosphate, manganese phosphate, ferric phosphate, lithium phosphate, ammonium dihydrogen phosphate, phosphoric acid, the one in vanadium phosphate or its combination;
Described carbon source material is: graphite, active carbon, Graphene, carbon nano-tube, Ke Qinhei, sucrose, glucose, the one in pitch or its combination.
The invention provides the method that two kinds are prepared described anode composite material.
Method (1) is Synchronos method, and preferred step comprises:
A () is by lithium source material, manganese source material, ferrous source material, vanadium source material, phosphate radical source material, carbon source material, be 1.10-2.00: 0.30-0.95: 0.00-0.38: 0.10-1.00: 1.10-2.00: 1.57-2.61 mixing by lithium, manganese, iron, vanadium, phosphorus, carbon molar ratio, add dispersant (as absolute ethyl alcohol or ethylene glycol), by ball mill process a period of time (as 1-10 hour), thus form the presoma through ball milling;
The b presoma through ball milling that step (a) obtains by () by heat treated, thus is formed through heat treated mixture;
In another preference, described step (b) comprises step:
(b-1) precursor that step (a) obtains is placed in tube furnace in 300-500 DEG C of heat treatment 3-20h, cools rear thus formed through 1 heat treated mixture;
(b-2) mixture that step (b-1) obtains is placed in tube furnace heat treatment 4-36h at 500-900 DEG C, thus is formed through 2 heat treated mixtures.
More preferably, also step is comprised between described step (b-1) and step (b-2): mixture step (b-1) obtained is through ball-milling treatment.
C mixture that step (b) obtains by (), cooling, thus form composite material of the present invention.
In another preference, also comprise step between step (b) and step (c): step (b) obtain after the cooling of heat treated mixture, mix with carbon source material, and by ball mill process, obtain the mixture through ball milling, wherein, the addition of described carbon source material is the 5%-20% of the weight of carbon source material in step (a).
Method (2) is asynchronous method, preferably, comprises step:
A () provides LiMn
1-xfe
xpO
4/ C and Li
3v
2(PO
4)
3/ C, wherein, x=0.00-0.40, described C are carbon-coating;
B () is according to y: the LiMn of molar ratio ball milling blend step (a) of (1-y)
1-xfe
xpO
4/ C and Li
3v
2(PO
4)
3/ C, wherein, x=0.00-0.40, y=0.50-0.95, thus form anode composite material of the present invention.
The equipment used during mixing in described step (b) can be any one mixing apparatus of this area routine, ball-grinding machine or disintegrating apparatus, preferably, is high energy ball mill and planetary ball mill.
Preferably, step (b) is by the LiMn of step (a)
1-xfe
xpO
4/ C and Li
3v
2(PO
4)
3/ C, according to y: after the molar ratio ball milling mixing of (1-y), carry out heat treated, thus form anode composite material of the present invention.
Preferably, described LiMn
1-xfe
xpO
4the preparation of/C comprises the following steps:
I () is by lithium source material, manganese source material, ferrous source material, phosphate radical source material, carbon source material, be 1.00: 0.60-0.95: 0-0.40: 1.00: 1.50-3.30 mixing by lithium, manganese, iron, phosphorus, carbon molar ratio, add dispersant (as absolute ethyl alcohol or ethylene glycol), by ball mill process a period of time (as 1-10 hour), obtain the presoma through ball milling;
(i-1) presoma that step (i) obtains is placed in tube furnace 300-500 DEG C of heat treatment 3-20h, obtains through 1 heat treated mixture after cooling;
(i-2) mixture that step (i-1) obtains is placed in tube furnace heat treatment 4-36h at 500-900 DEG C, obtains through 2 heat treated mixtures;
Preferably, comprise step after step (i-2): step (i-2) obtain after the cooling of heat treated mixture, mix with carbon source material, and by ball mill process, obtain the mixture through ball milling, wherein, the addition of described carbon source material is the 5%-20% of the weight of carbon source material in step (i).
(ii) mixture cooling step (ii-2) obtained, obtained LiMn
1-xfe
xpO
4/ C, wherein, x=0.00-0.40.
Preferably, described Li
3v
2(PO
4)
3the preparation of/C comprises the following steps:
A lithium source material, vanadium source material, phosphate radical source material, carbon source material are 3.00: 2.00: 3.00: 3.80-8.50 be placed in high energy ball mill by lithium, vanadium, phosphorus, carbon molar ratio by (), add dispersant, ball milling 2-10 hour obtained precursor;
B described precursor is placed in argon hydrogen gaseous mixture tube furnace 300-500 DEG C of heat treatment 3-15h by (), take out ball milling 2-10h;
C () is placed in argon hydrogen gaseous mixture tube furnace 500-900 DEG C of heat treatment 3-36h again, obtained Li
3v
2(PO
4)
3/ C.
Anode
Anode of the present invention contains anode composite material of the present invention;
Anode of the present invention can also contain conductive agent and binding agent, and wherein said conductive agent is acetylene black; Described binding agent is PVDF;
Preferred preparation method comprises step:
By anode composite material respectively with conductive agent, binding agent Homogeneous phase mixing in the solution (as nitrogen methyl pyrrolidone (NMP)), regulate the mass ratio (as 85: 10: 5) of suitable anode composite material, acetylene black and binding agent, then compressing tablet is applied on aluminium foil, obtained positive pole.
Lithium rechargeable battery
Lithium rechargeable battery provided by the invention, comprises positive electrode and negative material, and wherein, described positive electrode comprises phosphate anode composite material of lithium ion battery of the present invention.
Lithium rechargeable battery provided by the invention also comprises barrier film, electrolyte, shell.
Described negative material be native graphite, electrographite, carbonaceous mesophase spherules, carborundum, metal lithium sheet or lithium titanate material, described barrier film is PP & PE barrier film or fibreglass diaphragm, and described electrolyte is that lithium ion battery commonly uses electrolyte.
Owing to having two obvious voltage platforms, so can the discharge capacity of this monitoring battery.
Usefulness of the present invention is:
The maximum advantage of the present invention is that the composite material prepared has high potential platform 4.1V, high reversible capacity, good circulation stability, and electricity can monitoring function, and with low cost, the advantages such as environmental protection, possess the potentiality of the marketization.
(1) composite material of the present invention and metal lithium sheet are assembled into button cell, when 0.1C charge and discharge cycles, composite material first discharge capacity is 156mAh/g, the 0.5C discharge capacity first that circulates is 146mAh/g, the 1C discharge capacity first that circulates be 131mAh/g, the 2C discharge capacity first that circulates is 118mAh/g.Afterwards after 1C and 2C replaces charge and discharge cycles 110 times, 1C cyclic discharge capacity is 123mAh/g, and conservation rate is 94%, 2C cyclic discharge capacity be 118mAh/g conservation rate is 100%, illustrates excellent electrochemical properties.
(2) composite material of the present invention and lithium titanate are assembled into finished product button cell, and discharge capacity is 129mAh/g first, and have two discharge platforms, so can the discharge capacity of this monitoring battery.
Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the meaning be familiar with identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
The above-mentioned feature that the present invention mentions, or the feature that embodiment is mentioned can combination in any.All features that this case specification discloses can with any composition forms and use, each feature disclosed in specification, anyly can provide identical, alternative characteristics that is impartial or similar object replaces.Therefore apart from special instruction, the feature disclosed is only general example that is impartial or similar features.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, the usually conveniently conditioned disjunction condition of advising according to manufacturer.
The preparation of embodiment 1 phosphate anode composite material of lithium ion battery 1
A, get lithium dihydrogen phosphate, manganese carbonate, ferric oxalate, ammonium metavanadate, sucrose is raw material, is take raw material at 1.10: 0.95: 0.1: 1.10: 1.57 by lithium, manganese, vanadium, phosphorus, carbon molar ratio, be placed in mortar premix evenly after, add absolute ethyl alcohol and do dispersant, be put in high energy ball mill ball milling 4 hours obtained precursors.
B, the precursor of step a is put into tube furnace, heat up with the 5 DEG C/min rate of heat addition, pass into argon hydrogen gaseous mixture, be warmed up to 350 DEG C of roastings 8 hours;
C, by the product of step b take out be placed in planetary ball mill ball milling, do not add dispersant, rotating speed 400r/min, Ball-milling Time 2 hours.
D, the mixture of step c is put into tube furnace, heat up with the 5 DEG C/min rate of heat addition, pass into argon hydrogen gaseous mixture, be warmed up to 600 DEG C of roastings 15 hours; Naturally coldly rear taking-up mixture is removed.
E, the product of steps d to be taken out, add 20% carbon nano-tube, be placed in planetary ball mill ball milling, do not add dispersant, rotating speed 580r/min, Ball-milling Time 4 hours.
F, the mixture of step e taken out be placed in Muffle furnace and be heated to 220 DEG C, constant temperature 2 hours, naturally obtain 0.95LiMnPO after cooling
40.05Li
3v
2(PO
4)
3/ C composite 1.
The scanning electron microscope (SEM) photograph of composite material 1 is as shown in Figure 1A, 1B, and the particle diameter of composite material 1 is less than 700nm, and domain size distribution is relatively more even, and the diameter of minimum crystal grain is less than 100nm.The EDS distribution diagram of element of composite material 1 as shown in Figure 1 C, the component of arbitrarily small crystal grain is all made up of Mn, V, P, O, C, should be appreciated that, Li is also had (because elemental lithium atomic weight is too little in composite material component, EDS test can not detect elemental lithium, so EDS can not have elemental lithium peak in spectrogram).The x-ray diffraction pattern of composite material 1 as shown in figure ip, LiMnPO
4and Li
3v
2(PO
4)
3characteristic peak all clearly, illustrate in the composite, there is olivine LiMnPO
4and NASICONLi
3v
2(PO
4)
3two kinds of different structures.
The preparation of embodiment 2 phosphate anode composite material of lithium ion battery 2
A, get lithium dihydrogen phosphate, manganese carbonate, ferric oxalate, ammonium metavanadate, glucose is raw material, is take raw material at 2.00: 0.40: 0.10: 1.00: 2.00: 2.15 by lithium, manganese, iron, vanadium, phosphorus, carbon molar ratio, be placed in mortar premix evenly after, add absolute ethyl alcohol and do dispersant, be put in high energy ball mill ball milling 4 hours obtained precursors.
B, the precursor of step a is put into tube furnace, heat up with the 10 DEG C/min rate of heat addition, pass into high-purity argon gas, be warmed up to 450 DEG C of roastings 8 hours;
C, by the product of step b take out be placed in planetary ball mill ball milling, do not add dispersant, rotating speed 500r/min, Ball-milling Time 5 hours.
D, the mixture of step c is put into tube furnace, heat up with the 5 DEG C/min rate of heat addition, pass into argon hydrogen gaseous mixture, be warmed up to 550 DEG C of roastings 25 hours; Naturally coldly rear taking-up mixture is removed.
E, the product of steps d to be taken out, add 15% Ke Qinhei, be placed in planetary ball mill ball milling, do not add dispersant, rotating speed 580r/min, Ball-milling Time 5 hours.
F, the mixture of step e taken out be placed in Muffle furnace and be heated to 220 DEG C, constant temperature 2 hours, naturally obtain 0.5LiMn after cooling
0.8fe
0.2pO
40.5Li
3v
2(PO
4)
3/ C composite 2.
As shown in Figure 2 A, composite material particle diameter is 50-500nm to the scanning electron microscope (SEM) photograph of composite material 2, and domain size distribution is relatively more even, and minimum crystal grain diameter is less than 100nm.The x-ray diffraction pattern of composite material 2 as shown in Figure 2 B, LiMn
0.8fe
0.2pO
4and Li
3v
2(PO
4)
3characteristic peak all clearly, illustrate in the composite, there is olivine LiMn
0.8fe
0.2pO
4and NASICONLi
3v
2(PO
4)
3two kinds of different structures.
The preparation of embodiment 3 phosphate anode composite material of lithium ion battery 3
A, get lithium carbonate, ammonium dihydrogen phosphate, manganese carbonate, ferric oxalate, ammonium metavanadate, sucrose is raw material, be take raw material at 1.40: 0.72: 0.08: 0.40: 1.40: 1.65 by lithium, manganese, iron, vanadium, phosphorus, carbon molar ratio, be placed in mortar premix evenly after, add absolute ethyl alcohol and do dispersant, be put in high energy ball mill ball milling 4 hours obtained precursors.
B, the precursor of step a is put into tube furnace, heat up with the 8 DEG C/min rate of heat addition, pass into argon hydrogen gaseous mixture, be warmed up to 400 DEG C of roastings 10 hours;
C, by the product of step b take out be placed in planetary ball mill ball milling, do not add dispersant, rotating speed 450r/min, Ball-milling Time 4 hours.
D, the mixture of step c is put into tube furnace, heat up with the 8 DEG C/min rate of heat addition, pass into argon hydrogen gaseous mixture, be warmed up to 650 DEG C of roastings 15 hours; Naturally coldly rear taking-up mixture is removed.
E, the product of steps d to be taken out, add 15% acetylene black, be placed in planetary ball mill ball milling, do not add dispersant, rotating speed 500r/min, Ball-milling Time 5 hours.
F, the mixture of step e taken out be placed in Muffle furnace and be heated to 220 DEG C, constant temperature 2 hours, naturally obtain 0.8LiMn after cooling
0.9fe
0.1pO
40.2Li
3v
2(PO
4)
3/ C composite 3.
As shown in Figure 3A, composite material particle diameter is 100-800nm to the scanning electron microscope (SEM) photograph of composite material 3, and domain size distribution is relatively more even, and minimum size of microcrystal is less than 100nm.The x-ray diffraction pattern of composite material 3 as shown in Figure 3 B, LiMn
0.9fe
0.1pO
4and Li
3v
2(PO
4)
3characteristic peak all clearly, illustrate in the composite, there is olivine LiMn
0.9fe
0.1pO
4and NASICONLi
3v
2(PO
4)
3two kinds of different structures.
The preparation of embodiment 4 phosphate anode composite material of lithium ion battery 4
A, get lithium dihydrogen phosphate, manganese carbonate, glucose is raw material, be take raw material at 1.00: 1.00: 1.00: 1.50 by lithium, manganese, phosphorus, carbon molar ratio, be placed in mortar premix evenly after, add absolute ethyl alcohol and do dispersant, be put in high energy ball mill ball milling 4 hours obtained precursors.Precursor is put into tube furnace, heats up with the 10 DEG C/min rate of heat addition, pass into argon hydrogen gaseous mixture, be warmed up to 450 DEG C of roastings 8 hours; Product takes out and is placed in planetary ball mill ball milling, does not add dispersant, rotating speed 580r/min, Ball-milling Time 5 hours.Obtained mixture is put into tube furnace, passes into argon hydrogen gaseous mixture, be warmed up to 600 DEG C of roastings 20 hours; Naturally coldly rear taking-up mixture is removed.Product is taken out, adds 15%KB600EC (the black 600EC of Ke Qin), be placed in planetary ball mill ball milling, do not add dispersant, rotating speed 500r/min, Ball-milling Time 5 hours.Mixture taking-up is placed in Muffle furnace and is heated to 220 DEG C, constant temperature 2 hours, naturally obtained LiMnPO after cooling
4/ C composite 4a.
As shown in Figure 4 A, composite material particle diameter is 100-700nm to the scanning electron microscope (SEM) photograph of composite material 4a, and domain size distribution is relatively uniform.The x-ray diffraction pattern of composite material 4a as illustrated in figure 4f.
B, be take lithium dihydrogen phosphate at 3.00: 2.00: 3.00: 6.25 by lithium, vanadium, phosphorus, carbon molar ratio, vanadic oxide, active carbon, be placed in high energy ball mill ball milling 6 hours obtained precursors, be placed in argon hydrogen gaseous mixture tube furnace 300 DEG C of heat treatment 15h, after taking out ball milling 2h, be again placed in argon hydrogen gaseous mixture tube furnace 800 DEG C of heat treatment 10h, obtained Li
3v
2(PO
4)
3/ C composite 4b.
As shown in Figure 4 B, composite material domain size distribution is uneven for the scanning electron microscope (SEM) photograph of composite material 4b, and particle size range is at 200-2000nm, and particle is larger.The x-ray diffraction pattern of composite material 4b as illustrated in figure 4f.
C, get LiMnPO
4/ C and Li
3v
2(PO
4)
3/ C is 19: 1 mixing and ball milling 5h in molar ratio, obtained 0.95LiMnPO
40.05Li
3v
2(PO
4)
3/ C composite 4.
The scanning electron microscope (SEM) photograph of composite material 4 is as shown in Fig. 4 C, 4D, and the granule of composite material 4a is attached on the bulky grain of composite material 4b, and both are evenly distributed.As shown in Figure 4 E, any grain component contains the elements such as Mn, V, P, O, C to the EDS distribution diagram of element of composite material 4, and also should comprise Li (reason is with embodiment 1), the strong peak of 0 position is noise, is not element.As illustrated in figure 4f, Fig. 4 F contains the diffracting spectrum of composite material 4a and 4b to the x-ray diffraction pattern of composite material 4, and the not assorted peak of each sample, sample is very pure.Illustrate when prepared by asynchronous method compound, do not destroy respective lattice structure.
The preparation of embodiment 5 phosphate anode composite material of lithium ion battery 5
A, get lithium dihydrogen phosphate, manganese acetate, ferrous oxalate, glucose is raw material, be take raw material at 1.00: 0.80: 0.20: 1.00: 1.50 by lithium, manganese, phosphorus, carbon molar ratio, be placed in mortar premix evenly after, add absolute ethyl alcohol and do dispersant, be put in high energy ball mill ball milling 4 hours obtained precursors.Precursor is put into tube furnace, heats up with the 8 DEG C/min rate of heat addition, pass into argon hydrogen gaseous mixture, be warmed up to 400 DEG C of roastings 10 hours; Product takes out and is placed in planetary ball mill ball milling, does not add dispersant, rotating speed 500r/min, Ball-milling Time 5 hours.Obtained mixture is put into tube furnace, passes into argon hydrogen gaseous mixture, be warmed up to 600 DEG C of roastings 20 hours; Naturally coldly rear taking-up mixture is removed.Product is taken out, adds 15% carbon nano-tube, be placed in planetary ball mill ball milling, do not add dispersant, rotating speed 500r/min, Ball-milling Time 5 hours.Mixture taking-up is placed in Muffle furnace and is heated to 220 DEG C, constant temperature 2 hours, naturally obtained LiMn after cooling
0.8fe
0.2pO
4/ C composite 5a.
As shown in Figure 5A, composite material particle diameter is at 100-300nm, and even particle size distribution, without bulky grain for the scanning electron microscope (SEM) photograph of composite material 5a.The x-ray diffraction pattern of composite material 5a as illustrated in figure 5f.
B, be take lithium fluoride at 3.00: 2.00: 3.00: 3.8 by elemental mole ratios examples such as lithium, vanadium, phosphorus, carbon, ammonium metavanadate, ammonium dihydrogen phosphate, carbon nano-tube, be placed in high energy ball mill ball milling 6 hours obtained precursors, be placed in argon hydrogen gaseous mixture tube furnace 300 DEG C of heat treatment 15h, after taking out ball milling 2h, again be placed in argon hydrogen gaseous mixture tube furnace 800 DEG C of heat treatment 10h, obtained Li
3v
2(PO
4)
3/ C composite 5b.
As shown in Figure 5 B, composite material domain size distribution is uneven for the scanning electron microscope (SEM) photograph of composite material 5b, and particle size range is at 200-1000nm, and particle is larger.The x-ray diffraction pattern of composite material 5b as illustrated in figure 5f.
C, get LiMnPO
4/ C and Li
3v
2(PO
4)
3/ C is 4: 1 mixing and ball milling 5h in molar ratio, at 250 DEG C of heat treatment 4h, and obtained 0.8LiMn
0.8fe
0.2pO
40.2Li
3v
2(PO
4)
3/ C composite 5.
The scanning electron microscope (SEM) photograph of composite material 5 is as shown in Fig. 5 C, Fig. 5 D, and bulky grain is less, and phosphoric acid vanadium lithium part bulky grain is grated when mixing and ball milling.As shown in fig. 5e, the component of any crystal grain is all made up of Mn, Fe, V, P, O, C the EDS distribution diagram of element of composite material 5, also should comprise Li (reason is with embodiment 1).As illustrated in figure 5f, Fig. 5 F contains the diffracting spectrum of composite material 5a and 5b to the x-ray diffraction pattern of composite material 5, and the not assorted peak of each sample, sample is very pure.Illustrate when prepared by asynchronous method compound, do not destroy respective lattice structure.
6 preparations of embodiment 6 phosphate anode composite material of lithium ion battery
A, get lithium dihydrogen phosphate, manganese carbonate, iron oxide, sucrose is raw material, be take raw material at 1.00: 0.90: 0.10: 1.00: 1.80 by lithium, manganese, iron, phosphorus, carbon molar ratio, be placed in mortar premix evenly after, add absolute ethyl alcohol and do dispersant, be put in high energy ball mill ball milling 4 hours obtained precursors.Precursor is put into tube furnace, heats up with the 8 DEG C/min rate of heat addition, pass into argon hydrogen gaseous mixture, be warmed up to 400 DEG C of roastings 15 hours; Product takes out and is placed in planetary ball mill ball milling, does not add dispersant, rotating speed 500r/min, Ball-milling Time 5 hours.Obtained mixture is put into tube furnace, passes into argon hydrogen gaseous mixture, be warmed up to 650 DEG C of roastings 10 hours; Naturally coldly rear taking-up mixture is removed.Product is taken out, adds 15% Graphene, be placed in planetary ball mill ball milling, do not add dispersant, rotating speed 500r/min, Ball-milling Time 5 hours.Mixture taking-up is placed in Muffle furnace and is heated to 220 DEG C, constant temperature 2 hours, naturally obtained LiMn after cooling
0.9fe
0.1pO
4/ C composite 6a.
As shown in Figure 6A, composite material particle diameter is at 100-700nm, and domain size distribution is uneven for the scanning electron microscope (SEM) photograph of composite material 6a.The x-ray diffraction pattern of composite material 6a as shown in Figure 6 D.
B, be take lithium acetate at 3.00: 2.00: 3.00: 8.50 by lithium, vanadium, phosphorus, carbon molar ratio, ammonium metavanadate, ammonium dihydrogen phosphate, glucose, be placed in high energy ball mill ball milling 6 hours obtained precursors, be placed in argon hydrogen gaseous mixture tube furnace 300 DEG C of heat treatment 15h, after taking out ball milling 2h, again be placed in argon hydrogen gaseous mixture tube furnace 800 DEG C of heat treatment 10h, obtained Li
3v
2(PO
4)
3/ C composite 6b.
As shown in Figure 6B, composite material particle diameter is at 100-900nm, and domain size distribution is uneven, and bulky grain is more for the scanning electron microscope (SEM) photograph of composite material 6b.The x-ray diffraction pattern of composite material 6b as shown in Figure 6 D.
C, get LiMnPO
4/ C and Li
3v
2(PO
4)
3/ C is 1: 1 mixing and ball milling 5h in molar ratio, obtained 0.5LiMn
0.9fe
0.1pO
40.5Li
3v
2(PO
4)
3/ C composite 6.
As shown in Figure 6 C, bulky grain is less for the scanning electron microscope (SEM) photograph of composite material 6, and phosphoric acid vanadium lithium part bulky grain is grated when mixing and ball milling, bulky grain adsorbs a lot of granule.The x-ray diffraction pattern of composite material 6 as shown in Figure 6 D.
The preparation of embodiment 7 phosphate anode composite material of lithium ion battery 7
A, get lithium carbonate, ammonium dihydrogen phosphate, manganese carbonate, ferric oxalate, ammonium metavanadate, sucrose is raw material, be take raw material at 1.40: 0.64: 0.16: 0.40: 1.40: 1.65 by lithium, manganese, iron, vanadium, phosphorus, carbon molar ratio, be placed in mortar premix evenly after, add absolute ethyl alcohol and do dispersant, be put in high energy ball mill ball milling 4 hours obtained precursors.
B, the precursor of step a is put into tube furnace, heat up with the 5 DEG C/min rate of heat addition, pass into argon hydrogen gaseous mixture, be warmed up to 400 DEG C of roastings 12 hours;
C, by the product of step b take out be placed in planetary ball mill ball milling, do not add dispersant, rotating speed 580r/min, Ball-milling Time 3 hours.
D, the mixture of step c is put into tube furnace, heat up with the 8 DEG C/min rate of heat addition, pass into argon hydrogen gaseous mixture, be warmed up to 600 DEG C of roastings 15 hours; Naturally coldly rear taking-up mixture is removed.
E, the product of steps d to be taken out, add 15% acetylene black, be placed in planetary ball mill ball milling, do not add dispersant, rotating speed 500r/min, Ball-milling Time 3 hours.
F, the mixture of step e taken out be placed in Muffle furnace and be heated to 220 DEG C, constant temperature 2 hours, naturally obtain 0.8LiMn after cooling
0.8fe
0.2pO
40.2Li
3v
2(PO
4)
3/ C composite 7.
The scanning electron microscope (SEM) photograph of composite material 7 is as shown in Fig. 7 A, 7B, and composite material particle diameter, at below 400nm, is evenly distributed.The EDS distribution diagram of element of composite material 7 as seen in figure 7 c.The x-ray diffraction pattern of composite material 7 as illustrated in fig. 7d, composite material 7 has olivine and NASICON two kinds of different structures equally, does not have dephasign peak, illustrate in this synthetic system in diffraction maximum, two kinds of crystal structures can be compounded to form, again can not interfere generation dephasign mutually.
The preparation of embodiment 8 anode 1-8
The preparation of anode 1
By the anode composite material 1 prepared by embodiment 1 respectively with conductive agent acetylene black, binding agent Kynoar (PVDF) Homogeneous phase mixing in nitrogen methyl pyrrolidone (NMP) solution, the mass ratio of anode composite material, acetylene black and binding agent is respectively 85: 10: 5, then compressing tablet is applied on aluminium foil, obtained positive pole.
The preparation of anode 2
Preparation method, with the preparation method of anode 1, is anode composite material 2 prepared by embodiment 2 unlike anode composite material.
The preparation of anode 3
Preparation method, with the preparation method of anode 1, is anode composite material 3 prepared by embodiment 3 unlike anode composite material.
The preparation of anode 4
Preparation method, with the preparation method of anode 1, is anode composite material 4 prepared by embodiment 4 unlike anode composite material.
The preparation of anode 4a
Preparation method, with the preparation method of anode 1, is anode composite material 4a prepared by embodiment 4 unlike anode composite material.
The preparation of anode 5
Preparation method, with the preparation method of anode 1, is anode composite material 5 prepared by embodiment 5 unlike anode composite material.
The preparation of anode 6
Preparation method, with the preparation method of anode 1, is anode composite material 6 prepared by embodiment 6 unlike anode composite material.
The preparation of anode 6a
Preparation method, with the preparation method of anode 1, is anode composite material 6a prepared by embodiment 4 unlike anode composite material.
The preparation of anode 7
Preparation method, with the preparation method of anode 1, is anode composite material 7 prepared by embodiment 7 unlike anode composite material.
The preparation of embodiment 9 lithium battery 1-7
The preparation of lithium battery 1
By anode 1, take metal lithium sheet as negative pole, the ethylene carbonate of 1mol/L lithium hexafluoro phosphate and the solution of dimethyl carbonate are as electrolyte, and the polyethylene of 20 micron thickness is barrier film, are assembled into CR2032 type lithium coin cells 1.
The preparation of lithium battery 2
Preparation method, with the preparation method of lithium battery 1, replaces anode 1 unlike with anode 2.
The preparation of lithium battery 3
Preparation method, with the preparation method of lithium battery 1, replaces anode 1 unlike with anode 3.
The preparation of lithium battery 4
Preparation method, with the preparation method of lithium battery 1, replaces anode 1 unlike with anode 4.
The preparation of lithium battery 4a
Preparation method, with the preparation method of lithium battery 1, replaces anode 1 unlike with anode 4a.
The preparation of lithium battery 5
Preparation method, with the preparation method of lithium battery 1, replaces anode 1 unlike with anode 5.
The preparation of lithium battery 6
Preparation method, with the preparation method of lithium battery 1, replaces anode 1 unlike with anode 6.
The preparation of lithium battery 6a
Preparation method, with the preparation method of lithium battery 1, replaces anode 1 unlike with anode 6a.
The preparation of lithium battery 7
Preparation method, with the preparation method of lithium battery 1, replaces anode 1 unlike with anode 7.
The preparation of lithium battery 8
Preparation method with the preparation method of lithium battery 7, unlike taking lithium titanate as negative pole.
Embodiment 10
Lithium battery 4a, 6a and 7 chemical property compare
Method of testing is as follows:
The button cell be assembled into is on the electric charging-discharge tester system of indigo plant, carry out charge-discharge test, in 2.0-4.4V voltage range, first 4.4V is charged to battery 0.05C, carry out constant voltage charge at 4.4V, cut-off current is 0.01C, after static 1 minute, under 0.05C electric current, carry out constant-current discharge, cut-ff voltage is 2.0V.As a circulation, high rate cyclic is afterwards that charging and discharging currents is respectively 0.1C, 0.5C, 1C, 2C, and other condition is constant.
Test result: lithium battery 4a, 6a and 7 test result as shown in Figure 8:
Composite material 4a is plain lithium manganese phosphate, and reversible capacity is lower, and only has a voltage platform, the battery formed with this material, can not provide the signal of battery dump energy from voltage, can not early warning;
Composite material 6a is the lithium manganese phosphate of doped portion iron, and its discharge capacity obviously promotes.Doped portion iron not only increases the conductivity of material, and provide reversible capacity, also material is made to form two platforms, with the battery that this material makes for positive pole, output voltage has two sections of platforms, wherein second segment platform voltage as early warning voltage, can reduce battery protection system and judges battery dump energy difficulty;
Composite material 7 is the lithium manganese phosphate of doped portion iron and the composite material of phosphoric acid vanadium lithium, relative to composite material 6a, its discharge capacity has again obvious lifting, described composite material not only reversible capacity significantly improves, especially high-multiplying power discharge capacity improves obviously, and its high rate cyclic stability strengthens, and has lithium manganese phosphate and the two-part advantage of phosphoric acid vanadium lithium of doped portion iron concurrently, has possessed the chemical property making battery.
This composite material voltage platform major part is at 4.1V, and relative to the LiFePO 4 material of 3.4V, voltage platform improves 0.7V, and the energy density of battery prepared by this composite material is higher, and this is one of advantage of the present invention.
The electrochemical property test of lithium battery 8
Method of testing is the same
The test result of lithium battery 8: as shown in Figure 9, this battery system has the output voltage of 2.4V, the energy density of battery is higher (relative to LiFePO4/lithium titanate battery 1.8V), lithium battery 8 first discharge capacity is 129mAh/g, and have two discharge platforms, so electricity warning function can be provided according to voltage difference.
The chemical property contrast of the anode composite material prepared by embodiment 11 embodiment 1-7
Lithium battery preparation method
Get composite material, conductive agent (Surper-P) and PVDF (Kynoar), according to mass ratio be 80: 10: 10 mixing, add after NMP (1-METHYLPYRROLIDONE) mixes, be coated on aluminium foil, after 120 DEG C of vacuumizes, cut into sheet-punching machine the disk that diameter is 1.4cm, in high-purity argon gas glove box, be that 16mm metal lithium sheet is done electrode with diameter, select PP/PE barrier film, add suitable electrolyte (1mol/LLiPF
6+ EC+DMC, wherein volume ratio EC: DMC=1: 1), select 2032 button cell shells encapsulation, obtained button cell.
Electrochemical property test
The button cell be assembled into is on the electric charging-discharge tester system of indigo plant, carry out charge-discharge test, in 2.0-4.4V voltage range, first 4.4V is charged to battery 0.05C, carry out constant voltage charge at 4.4V, cut-off current is 0.01C, after static 1 minute, under 0.05C electric current, carry out constant-current discharge, cut-ff voltage is 2.0V.As a circulation, high rate cyclic is afterwards that charging and discharging currents is respectively 0.1C, 0.5C, 1C, 2C, and other condition is constant.
Test result, as shown in Fig. 1 E, 4G, 5G, 7E and table 1.
Composite material 1: although x, y value of this composite material is for being border proportioning, its discharge capacity is higher, and cyclical stability, well especially when high-discharge-rate, has good application potential in electrochemistry.
Composite material 2: this composite material discharge capacity is high, and under each discharge-rate, cyclical stability is all very good, has good application potential in electrochemistry.
Composite material 3: this composite material discharge capacity is high, and under each discharge-rate, cyclical stability is better, has good application potential in electrochemistry.
Composite material 4a: composite material 4a capacitance loss is relatively serious, especially during high rate cyclic, discharge capacity very low (as 2C first discharge capacity be 39mAh/g, be 32mAh/g after 120 circulations, conservation rate is 82.1%), chemical property is poor.
Composite material 4b: the chemical property of pure phase phosphoric acid vanadium lithium is better than pure phase lithium manganese phosphate, but its cyclic discharge capacity has much room for improvement.
Composite material 4: the chemical property of this composite material is better than bi-material chemical property separately (especially discharge capacity aspect), has good application potential in electrochemistry.
Composite material 5a: when high rate cyclic, discharge capacity obviously reduces, and chemical property is poor.Relatively composite material 4a, after doped portion ferro element, under low range, material discharging capacity obviously promotes, and high rate cyclic stability promotes, but discharge capacity promotes not obvious.
Composite material 5b: the chemical property of pure phase phosphoric acid vanadium lithium is better than pure phase lithium manganese phosphate, but its discharge capacity has much room for improvement.
Composite material 5: the chemical property of composite material 5 is obviously better than bi-material chemical property separately (especially discharge capacity aspect).
Composite material 6a: when high rate cyclic, discharge capacity obviously reduces, and chemical property is poor.
Composite material 6b: when high rate cyclic, discharge capacity obviously reduces, and chemical property is poor.The chemical property of pure phase phosphoric acid vanadium lithium is better than pure phase lithium manganese phosphate, but its discharge capacity has much room for improvement.
Composite material 6: this composite material not only improves the reversible capacity of material, and when high rate cyclic, cycle performance obviously improves, than bi-material chemical property separately more excellent.
Composite material 7: this composite material cyclical stability is good, and discharge capacity is higher, has good application potential in electrochemistry.
Composite material 5 and composite material 7 have similarly chemical constituent, composite material 5 is asynchronous preparation method normal temperature physical mixed heat treatment combination process, composite material 7 is synchronous preparation method high temperature combination process, illustrates that synchronous preparation method high temperature combination process obtains material and has good chemical property.
Table 1 discharge capacity contrast table
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.
Claims (12)
1. a phosphate anode composite material of lithium ion battery, is characterized in that, described composite material comprises crystal grain and is coated on the carbon-coating outside crystal grain, and wherein said crystal grain has following lattice structure: LiMn
1-xfe
xpO
4lattice structure and Li
3v
2(PO
4)
3lattice structure, in formula, x=0.05-0.35;
And the chemical formula of described composite material is yLiMn
1-xfe
xpO
4(1-y) Li
3v
2(PO
4)
3/ C, wherein, x=0.05-0.35, y=0.50-0.95, described C is carbon-coating;
Described LiMn
1-xfe
xpO
4lattice structure is olivine structural, and described Li
3v
2(PO
4)
3for NASICON structure;
And described LiMn
1-xfe
xpO
4or Li
3v
2(PO
4)
3particle diameter be 10nm-5000nm.
2. anode composite material as claimed in claim 1, is characterized in that, y=0.55-0.90.
3. anode composite material as claimed in claim 1, is characterized in that, x=0.10-0.20.
4. anode composite material as claimed in claim 1, is characterized in that, described LiMn
1-xfe
xpO
4or Li
3v
2(PO
4)
3particle diameter be 10nm-500nm.
5. an anode, is characterized in that, described positive pole contains anode composite material according to claim 1.
6. anode as claimed in claim 5, is characterized in that, described positive pole is also containing conductive agent and binding agent.
7. a lithium rechargeable battery, is characterized in that, described battery contains anode according to claim 5.
8. a lithium rechargeable battery, it is characterized in that, described lithium rechargeable battery comprises positive electrode, negative material, barrier film, electrolyte and shell, and wherein, described positive electrode comprises phosphate anode composite material of lithium ion battery according to claim 1.
9. a preparation method for anode composite material as claimed in claim 1, is characterized in that, comprise step:
A () is by lithium source material, manganese source material, ferrous source material, vanadium source material, phosphate radical source material, carbon source material, be 1.10-2.00:0.325-0.9025:0.025-0.3325:0.10-1.00:1.10-2.00: 1.57-2.61 mixing by lithium, manganese, iron, vanadium, phosphorus, carbon molar ratio, add dispersant, by ball mill process, thus form the presoma through ball milling;
The b presoma through ball milling that step (a) obtains by () by heat treated, thus is formed through heat treated mixture;
C mixture cooling that step (b) obtains by (), thus form anode composite material according to claim 1;
And also comprise step between step (b) and step (c): step (b) obtain after the cooling of heat treated mixture, mix with carbon source material, and by ball mill process, obtain the mixture through ball milling, wherein, the addition of described carbon source material is the 5%-20% of the weight of carbon source material in step (a).
10. preparation method as claimed in claim 9, it is characterized in that, described step (b) comprises step:
(b-1) precursor that step (a) obtains is placed in tube furnace in 300-500 DEG C of heat treatment 3-20h, cools rear thus formed through 1 heat treated mixture;
(b-2) mixture that step (b-1) obtains is placed in tube furnace heat treatment 4-36h at 500-900 DEG C, thus is formed through 2 heat treated mixtures.
The preparation method of 11. 1 kinds of anode composite materials as claimed in claim 1, is characterized in that, comprises step:
A () provides LiMn
1-xfe
xpO
4/ C and Li
3v
2(PO
4)
3/ C, wherein, x=0.05-0.35, described C are carbon-coating;
B () is according to y:(1-y) the LiMn of molar ratio ball milling blend step (a)
1-xfe
xpO
4/ C and Li
3v
2(PO
4)
3/ C, wherein, x=0.05-0.35, y=0.50-0.95, thus form anode composite material according to claim 1;
Further, described LiMn
1-xfe
xpO
4/ C, wherein, x=0.05-0.35, its preparation comprises the following steps:
I () is by lithium source material, manganese source material, ferrous source material, phosphate radical source material, carbon source material, be 1.00:0.65-0.95:0.05-0.35:1.00:1.50-3.30 mixing by lithium, manganese, iron, phosphorus, carbon molar ratio, add dispersant, by ball mill process, obtain the presoma through ball milling;
(i-1) presoma that step (i) obtains is placed in tube furnace 300-500 DEG C of heat treatment 3-20h, obtains through 1 heat treated mixture after cooling;
(i-2) mixture that step (i-1) obtains is placed in tube furnace heat treatment 4-36h at 500-900 DEG C, obtains through 2 heat treated mixtures;
(ii) mixture cooling step (ii-2) obtained, obtained LiMn
1-xfe
xpO
4/ C, wherein, x=0.05-0.35;
And also comprise step between step (i-2) and step (ii): step (i-2) obtain after the cooling of heat treated mixture, mix with carbon source material, and by ball mill process, obtain the mixture through ball milling, wherein, the addition of described carbon source material is the 5%-20% of the weight of carbon source material in step (i).
The purposes of 12. 1 kinds of composite materials as claimed in claim 1, is characterized in that, for the preparation of lithium rechargeable battery.
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| CN104332614B (en) * | 2014-09-05 | 2017-09-26 | 中南大学 | A kind of nucleocapsid structure lithium ion battery anode composite material and preparation method thereof |
| CN104300110B (en) * | 2014-09-23 | 2016-11-16 | 中南大学 | The preparation method of lithium manganese phosphate-phosphoric acid vanadium lithium composite |
| CN105633366A (en) * | 2015-12-30 | 2016-06-01 | 镇江宜能新能源材料科技有限公司 | C and lithium-vanadium oxide conducting layer-cocoated lithium ferric manganese phosphate cathode material and preparation method thereof |
| CN105576217B (en) * | 2016-03-17 | 2018-04-03 | 齐鲁工业大学 | A kind of preparation method of the phosphate cathode material of three-dimensional carbon in-stiu coating |
| CN107768611A (en) * | 2016-08-23 | 2018-03-06 | 宁德时代新能源科技股份有限公司 | Modified positive electrode material, preparation method thereof and secondary battery |
| CN106299285A (en) * | 2016-09-08 | 2017-01-04 | 天津理工大学 | A kind of phosphate composite positive pole of high safety performance and preparation method thereof |
| CN106450239B (en) * | 2016-12-08 | 2019-06-14 | 深圳市鑫永丰科技有限公司 | A kind of iron manganese phosphate for lithium composite material and preparation method and lithium ion battery |
| CN107706361A (en) * | 2017-08-14 | 2018-02-16 | 宁波维科新能源科技有限公司 | A kind of ternary compound potassium ion electrokinetic cell |
| CN107978743B (en) * | 2017-11-20 | 2020-07-24 | 中南大学 | Sodium-ion battery positive electrode material, preparation method thereof and sodium-ion battery |
| CN108172794B (en) * | 2017-12-27 | 2020-02-21 | 中科廊坊过程工程研究院 | Composite cathode material and preparation method and application thereof |
| CN110611080B (en) * | 2018-06-15 | 2021-03-12 | 中南大学 | Transition metal doped titanium manganese phosphate sodium/carbon composite positive electrode material, preparation thereof and application thereof in sodium ion battery |
| CN111564622A (en) * | 2020-07-14 | 2020-08-21 | 天能帅福得能源股份有限公司 | Lithium manganese iron phosphate cathode material and preparation method thereof |
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| CN102208620A (en) * | 2011-04-19 | 2011-10-05 | 哈尔滨工业大学 | Method for preparing lithium ion battery anode material xLiFePO4.yLi3V2(PO4)3 |
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