CN109713238A - A kind of lithium ion cell positive additive - Google Patents
A kind of lithium ion cell positive additive Download PDFInfo
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- CN109713238A CN109713238A CN201711012468.2A CN201711012468A CN109713238A CN 109713238 A CN109713238 A CN 109713238A CN 201711012468 A CN201711012468 A CN 201711012468A CN 109713238 A CN109713238 A CN 109713238A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses the rare earth doped lithium ion cell positive additives of the one kind for belonging to clean energy technology field.The anode additive has with general formula Li5+aFexAyBzO4The chemical composition of expression, 0≤x≤1,0≤y≤1,0 a≤2 < z≤0.1, x+y+z=1,0 <.The relatively broad anode additive Li with research5FeO4It compares, to material doped thulium, can be improved the high rate performance of material.Meanwhile the multi-element compounds Li formed after the elements such as the doping of transition metal element position Co, Mn, Zn, Ir, Pt, Ni5+aFexAyBzO4, can effectively reduce platform voltage.By the additive application in full battery, it can achieve the effect that improve battery energy density, high rate performance and service life.
Description
Technical field
The invention belongs to clean energy technology fields, and in particular to the rare earth doped lithium ion cell positive of one kind adds
Add object.
Background technique
Lithium ion battery is widely used in all trades and professions because having high-energy density and service life cycle.With society
The progress that can develop, to the energy density of lithium ion battery, more stringent requirements are proposed, therefore also brings newly to lithium electricity industry
Challenge.During the initial charge of battery, the formation of solid electrolyte film (SEI film) can consume part lithium, to cause
The loss of lithium ion in positive electrode, leads to the reduction of battery reversible capacity.
Document (Chem.Chem.Phys., 2014,16,22073) is to Li5FeO4Theoretical calculation has been carried out, has obtained the material
Theoretical specific capacity (867mAh/g) with higher, therefore widely paid close attention to by people, it is believed that it may be used as anode additive
It uses, the lithium consumed during supplement battery initial charge due to the formation of solid electrolyte film (SEI film).However Li5FeO4
Due to wide band gap (about 3.0eV), causing it in same type of material with lower electronic conductance and poor forthright again
Energy.In addition, it is found that the charging voltage when battery is greater than from document (Int.J.Electrochem.Sci., 2013,8,6393)
When 5.0V, Li5FeO4Lithium could be sufficiently taken off, makes its actual capacity close to theoretical capacity.And the voltage of present most of positive electrodes
SC service ceiling is below 4.5V, and the electrochemical window of common electrolyte is not able to satisfy the requirement of high voltage, high voltage at present
Under will lead to electrolyte and be oxidized decomposition, shorten the service life of battery.Li5FeO4The poor high rate performance of material and high
SC service ceiling voltage seriously limits it in the application of field of lithium ion battery.
Summary of the invention
The purpose of the present invention is to provide a kind of lithium ion cell positive additives.
In order to improve Li5FeO4High rate performance, reduce its SC service ceiling voltage, make its electricity actually available in lithium battery
High capacity is played in pressure range, its Fe can be doped.Since rare earth element has biggish ionic radius, into crystalline substance
After lattice replace part transition metal element, the diffusion admittance of lithium ion can be expanded, thus promote product have faster lithium from
Son insertion and ability of moving out can achieve the effect that improve material high rate performance.In addition, being learnt by theoretical calculation, Li6ZnO4,
Li6CoO4, Li6MnO4、Li8IrO6, Li8PtO6Equal compounds and Li5FeO4Crystal structure (antifluorite structure) having the same.
But in its charge and discharge process, but have than Li5FeO4Lower voltage platform (~2.9V), using members such as Zn, Co, Mn, Ir, Pt
Element is to Li5FeO4It is doped or replaces, be capable of forming polynary antifluorite structure, to achieve the purpose that reduce material voltage.
A kind of lithium ion cell positive additive, general formula are represented by Li5+aFexAyBzO4, in which: 0≤x≤1,0≤y
≤ 1,0 a≤2 < z≤0.1, x+y+z=1,0 <.
Any one or more of the A in Co, Mn, Zn, Ir, Pt, Ni；The B be selected from La, Ce, Pr, Nd, Sm,
Any one or more in Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb rare earth element.
The preparation method of above-mentioned lithium ion cell positive additive, by atomic molar ratio by lithium source, source of iron, transition metal
Source, rare-earth compound after mixing, are made after 700~900 DEG C of 2~60h of heat preservation are warming up under protective atmosphere.
The lithium source is lithia, lithium carbonate, lithium nitrate, lithium acetate, lithium oxalate, lithium hydroxide, one of lithium alkylide
Or several combination.
The source of iron be alpha-ferric oxide, beta oxidation iron, ferroso-ferric oxide, ferric sulfate, ferric nitrate, iron hydroxide, iron chloride,
One or more of ferric acetate.
The transition metal source is oxidation of interim metal, sulfide, nitride, disulphide, phosphide, hydrogen-oxygen
One or more of compound, chloride.
The rare-earth compound is the nitrate of rare earth element, sulfate, oxide, hydroxide, in chloride
One or more.
A kind of non-aqueous batteries, including positive active material, negative electrode active material, positive and negative anodes collector, electrolyte, every
Film, tab and aluminum plastic film outer packing.
The positive active material include claim 1 described in lithium ion cell positive additive, content be 0.01~
10%.
Beneficial effects of the present invention: additive of the invention can obtain higher capacity charging to 4.5V or less, and
With more excellent high rate performance.It is applied to full battery system in the form of anode additive, anode can not changed
Under the use condition of material and electrolyte, achieve the purpose that improve battery energy density and high rate performance.
Detailed description of the invention
Fig. 1 is the structure chart for indicating Soft Roll non-aqueous batteries；(a) it is appearance diagram, (b) is that section illustrates (c) to be (a)
In along the face 8-8 cross-sectional view.
Fig. 2 is Li prepared by embodiment 15Fe0.998Gd0.002O4, Li prepared by embodiment 25Fe0.995La0.005O4, embodiment
Li prepared by 86.2Co0.9Ir0.094Eu0.006O4The XRD spectrum comparison diagram of anode additive.
Fig. 3 is Li prepared by comparative example 15FeO4With Li prepared by embodiment 55.9Fe0.5Pt0.2Zn0.291-Sm0.009O4Anode
The SEM image of additive.
Fig. 4 is Li prepared by comparative example 1 under 0.05C multiplying power5FeO4With anode additive prepared by embodiment 6
Li5.8Fe0.2Co0.7Zn0.092Gd0.008O4Chemical property map.
Fig. 5 is LiNi0.333Co0.333Mn0.333O2After the M6 of middle incorporation 4%, 6%, 8%, under 0.05C multiplying power, 3-4.3V electricity
Press gram volume-voltage curve to lithium button half-cell charge and discharge in range.
Fig. 6 is full battery prepared by comparative example 2 and embodiment 13 under 0.05C multiplying power, in 2.6-4.2V voltage range
Charge and discharge gram volume-voltage curve.
Specific embodiment
Anode additive described in following embodiments: anode additive used is with general formula Li5+aFexAyBzO4The chemistry of expression
Composition, 0≤x≤1,0≤y≤1,0 a≤2 < z≤0.1, x+y+z=1,0 <, wherein A is in Co, Mn, Zn, Ir, Pt, Ni
Any one or more, preferably Co, Mn, Zn.B be expressed as include La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
Any one or more in the rare earth elements such as Yb, preferably Gd, Nd.The incorporation of rare earth element can make material obtain higher energy
Density and species activity, doping molar ratio are 0~0.01.
The anode additive uses solid-phase synthesis well known in the art, in molar ratio by lithium source, source of iron, transition metal
Source, rare-earth compound after mixing, are made after 700~900 DEG C of 2~60h of heat preservation are warming up under protective atmosphere.Wherein
The lithium source is one or more of lithia, lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium nitrate or lithium alkylide
Combination.The source of iron is alpha-ferric oxide, in beta oxidation iron, ferroso-ferric oxide, ferric sulfate, ferric nitrate, iron hydroxide, iron chloride
It is one or more of.The transition metal source be oxidation of interim metal, sulfide, nitride, disulphide, phosphide,
One or more of hydroxide, chloride.The rare-earth compound is the nitrate of rare earth element, sulfate, oxygen
One or more of compound, hydroxide, chloride.The protective atmosphere is the inert atmospheres such as nitrogen, argon gas.
Non-aqueous batteries: nonaqueous electrolyte battery has: anode, cathode, collector, electrolyte, diaphragm, tab and plastic-aluminum
Film outer packing.
1) positive
Anode has: collector and be formed in the one or both sides of the collector and include active material, conductive agent and
The anode layer of binder.Wherein positive active material includes positive electrode and positive electrode additive.
Positive electrode complex Li-Mn-oxide commonly used in the art (such as Li can be used in positive active materialxMn2O4Or
LixMnO2), lithium nickel composite oxide (such as LixNiO2), lithium cobalt composite oxide (LixCoO2), lithium/nickel/cobalt composite oxide
(such as LiNi1-yCoyO2), lithium manganese cobalt composite oxide (such as LixMnyCo1-yO2), lithium manganese cobalt nickel composite oxides (such as
LixMnyCozNi1-x-yO2), lithium manganese cobalt aluminum composite oxide (such as LixMnyCozAl1-x-yO2), spinel type lithium & manganese nickel composite oxygen
Compound (LixMn2-yNiyO4), (such as the Li of the Lithium Phosphor Oxide with olivine structuralxFePO4、LixFe1-yMnyPO4、
LixCoPO4).(here, x, y, z is preferably 0 x≤1 <, 0≤y≤1,0≤z≤1,0≤y+z≤1).Further preferred activity
Substance is lithium manganese cobalt nickel composite oxides or lithium manganese cobalt aluminum composite oxide.
Anode activity substance additive is added in anode sizing agent during positive slurry.Supplement battery is played to fill for the first time
The effect of the lithium ion of discharge process loss, to improve the cycle efficieny of battery.Mixed ratio is 0.01~10wt%.
Conductive agent improves the current collection performance of active material, reduces the contact resistance with collector.Conductive agent commonly used in the art
Include the Carbonaceous matters such as acetylene black, carbon black, graphite, carbon nanotube, graphene, carbon nano-fiber (VGCF).
Binder bonds active material and conductive agent.Binder commonly used in the art includes polytetrafluoroethylene (PTFE) (PTFE), gathers
Vinylidene (PVDF), fluorine-containing rubber etc..
Active material, conductive agent and binder in anode layer preferably respectively with 70~98wt%, 1~15wt% and 1~
The ratio of 15wt% is cooperated.
Collector is the alloy foil of aluminium foil or the element comprising Mg, Ti, Zn, Mn, Fe, Cu, Si etc.
Positive making step is pole piece making step commonly used in the art: active material, conductive agent and binder are suspended in
Slurry is prepared in general solvent, which is coated on the current collector and is dried, then pressurizes, thus makes
Anode.
2) cathode
Cathode has: collector and be formed in the one or both sides of the collector and include active material, conductive agent and
The negative electrode layer of binder.Negative electrode active material is commonly used in the art with embedding lithium position compound.It is preferred that silicon systems, the compound system of silicon-carbon
Material and hard carbon material.Remaining each component part of cathode pole piece and pole piece preparation method are identical as anode.
3) non-aqueous electrolyte
Non-aqueous electrolyte well known in the art, such as lithium perchlorate (LiClO can be enumerated4), lithium hexafluoro phosphate
(LiPF6), LiBF4 (LiBF4), hexafluoroarsenate lithium (LiAsF6), trifluoromethanesulfonic acid lithium (LiCF3SO3), bis- (trifluoro methylsulphurs
Acyl) imine lithium [LiN (CF3SO2)2] lithium salts or mixture comprising these.Electrolyte is preferably not easy under high potential
The substance of oxidation, most preferably LiPF6.The example of organic solvent includes propylene carbonate (PC), ethylene carbonate (EC), carbonic acid Asia
The cyclic carbonate of vinyl acetate etc；Diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) etc
Linear carbonate；The ring-type of tetrahydrofuran (THF), 2- methyltetrahydrofuran (2MeTHF), dioxolane (DOX) etc
Ether；The chain ether of dimethoxy-ethane (DME), diethoxyethane (DEE) etc；Or gamma-butyrolacton (GBL), acetonitrile (AN),
Sulfolane (SL).These organic solvents can use individually or in the form of mixed solvent.
4) diaphragm
Diaphragm well known in the art can be enumerated containing such as polyethylene, polypropylene, cellulose or Kynoar
(PVDF) porous film or synthetic resin non-woven fabrics.Preferred porous film is made by polyethylene or polypropylene, by
It can be melted at a certain temperature in it and block electric current, it is thus possible to improve safety.
Non-aqueous batteries production method: non-aqueous soft-package battery comprising battery main body, tab, aluminum plastic film and polypropylene
(PP) protection board, it is characterised in that tab is drawn by two sides, is conducive to radiate.The PP protection board wraps electricity with adhesive tape
Tank main body, it is not Chong Die with positive and negative anodes tab.
As Fig. 1 (a) illustrates: a kind of soft-package battery 1, it includes tab 2, ontology 3, laminated aluminum film 5, in edge part 5
With striated hot pressing structure 4.Striated hot pressing trace is located at the one of side of soft-package battery 1 and out tab side, ontology 3 by
Dotted line is shown.Fig. 1 (b) is the diagrammatic cross-section of Fig. 1, and tab 2 is connected in a manner of spot welding with the area 6 that is left white of pole piece, 7 table in figure
Show Welding Area.Fig. 1 (c) is the cross-sectional view in Fig. 1 (a) along 8-8 planes.As seen from the figure: battery main body 3 is by diaphragm
9, cathode 10, anode 11, PCB protection board 12 form.Main body is stacked by positive and negative anodes intersection.Cathode 11 is wrapped by diaphragm 9,
It is left white unified towards unified direction.Anode is placed among two groups of cathode with diaphragm package, is left white unified direction and is left white with cathode
Opposite direction.
Below by embodiment, the present invention is further described in detail.In addition, without departing from master of the invention
Purport is just not limited to the embodiment of following record.
Embodiment 1
By LiOH, α-Fe2O3, Gd2O3According to molar ratio Li:Fe:Gd=5:0.998:0.002, it is enterprising to be placed into ball mill
Row mixing will be placed into crucible after the sieving of mixed powder, crucible be put into atmosphere furnace, nitrogen is passed through, with 8 DEG C/min
Speed be heated to 840 DEG C keep the temperature 8 hours, be made additive M1 be Li5Fe0.998Gd0.002O4, the XRD spectrum of embodiment 1 is shown in figure
2。
Embodiment 2
By LiNo3, Fe (No3)3, La2O3According to molar ratio Li:Fe:La=5:0.995:0.005, it is placed on ball mill
Mixed, will mixed powder sieving after be placed into crucible, crucible is put into atmosphere furnace, nitrogen is passed through, with 8 DEG C/
The speed of min is heated to 820 DEG C and keeps the temperature 20 hours, and it is Li that additive M2, which is made,5Fe0.995La0.005O4。
Embodiment 3
By Li2O, α-Fe2O3, Ir2O3, Eu2O3According to molar ratio Li:Fe:Ir:Eu=6.5:0.5:0.494:0.006, put
It sets and is mixed on ball mill, will be placed into crucible after the sieving of mixed powder, crucible is put into atmosphere furnace, is passed through
Argon gas is heated to 830 DEG C with the speed of 8 DEG C/min and keeps the temperature 8 hours, and it is Li that additive M3, which is made,6.5Fe0.5Ir0.494Eu0.006O4。
Embodiment 4
By Li2O, α-Fe2O3, ZnO, Er2O3According to the ratio of molar ratio Li:Fe:Zn:Er=5.6:0.4:0.592:0.008
It after example mixing, is placed on ball mill and is mixed, will be placed into crucible after the sieving of mixed powder, crucible is put into gas
In atmosphere furnace, it is passed through nitrogen, 820 DEG C is heated to the speed of 8 DEG C/min and keeps the temperature 48 hours, additive M4, which is made, is
Li5.6Fe0.4Zn0.592Er0.008O4。
Embodiment 5
By Li2CO3, α-Fe2O3, ZnO, PtO2, Sm2O3According to molar ratio Li:Fe:Pt:Zn:Sm=5.9:0.5:0.2:
It after the ratio mixing of 0.291:0.009, is placed on ball mill and is mixed, crucible will be placed into after the sieving of mixed powder
In, crucible is put into atmosphere furnace, nitrogen is passed through, 820 DEG C is heated to the speed of 8 DEG C/min and keeps the temperature 10 hours, addition is made
Agent M5 is Li5.9Fe0.5Pt0.2Zn0.291Sm0.009O4, the SEM spectrum of embodiment 5 is shown in Fig. 3.
Embodiment 6
By Li2O, α-Fe2O3, CoO, ZnO, Gd2O3According to molar ratio Li:Fe:Co:Zn:Gd=5.8:0.2:0.7:
It after the ratio mixing of 0.092:0.008, is placed on ball mill and is mixed, crucible will be placed into after the sieving of mixed powder
In, crucible is put into atmosphere furnace, nitrogen is passed through, 790 DEG C is heated to the speed of 8 DEG C/min and keeps the temperature 60 hours, addition is made
Agent M6 is Li5.8Fe0.2Co0.7Zn0.092Gd0.008O4, the XRD curve of embodiment 6 is shown in that Fig. 2, chemical property curve are shown in Fig. 4.
Embodiment 7
By Li2O, α-Fe2O3, MnO, CoSO4, Eu2O3According to a mole Li:Fe:Mn:Co:Eu=5.7:0.3:
After the ratio mixing of 0.3:0.392:0.008, it is placed on ball mill and is mixed, mixed powder is sieved
After be placed into crucible, crucible is put into atmosphere furnace, nitrogen is passed through, it is 72 small to be heated to 800 DEG C of heat preservations with the speed of 5 DEG C/min
When be made additive M7 be Li5.7Fe0.3Mn0.3Co0.392Eu0.008O4。
Embodiment 8
By LiOH, Co (OH)2,Ir2O3, Eu2O3According to molar ratio Li:Co:Ir:Eu=6.2:0.9:0.094:0.006's
It after ratio mixing, is placed on ball mill and is mixed, will be placed into crucible after the sieving of mixed powder, crucible is put into
In atmosphere furnace, it is passed through nitrogen, being heated to 700 DEG C of heat preservations, 8 hours obtained additive M8 with the speed of 10 DEG C/min is
Li6.2Co0.9Ir0.094Eu0.006O4。
Embodiment 9
By Li2CO3, ZnO, MnO, Eu2O3It is mixed according to the ratio of molar ratio Li:Zn:Mn:Eu=6:0.5:0.494:0.006
It after conjunction, is placed on ball mill and is mixed, will be placed into crucible after the sieving of mixed powder, crucible is put into atmosphere furnace
In, it is passed through nitrogen, being heated to 780 DEG C of heat preservations, 48 hours obtained additive M9 with the speed of 10 DEG C/min is
Li6Zn0.5Mn0.494Eu0.006O4。
Embodiment 10
By Li2CO3, CoO, MnO, Eu2O3It is mixed according to the ratio of molar ratio Li:Co:Mn:Gd=6:0.5:0.494:0.006
It after conjunction, is placed on ball mill and is mixed, will be placed into crucible after the sieving of mixed powder, crucible is put into atmosphere furnace
In, it is passed through nitrogen, being heated to 750 DEG C of heat preservations, 12 hours obtained additive M10 with the speed of 10 DEG C/min is
Li6Co0.5Mn0.494Gd0.006O4。
Comparative example 1
By LiOH, α-Fe2O3It is placed on ball mill and is mixed with the ratio of molar ratio Li:Fe=5:1, after mixing
Powder sieving after be placed into crucible, crucible is put into atmosphere furnace, nitrogen is passed through, is heated to 780 with the speed of 8 DEG C/min
DEG C heat preservation 10 hours, be made anode additive S1 be Li5FeO4.The SEM spectrum and electrochemical profiles of comparative example 1 are shown in Fig. 3 and Fig. 4.
To Examples 1 to 10 and the obtained anode additive of comparative example 1, it is fabricated to lithium button half-cell, 25 DEG C of rooms
Tested under temperature, test voltage be 3.0~4.5V, multiplying power 0.05C, charge specific capacity and to lithium voltage platform test tie
Fruit is shown in following table 1.
Table 1
As can be seen that incorporation rare earth element multicomponent material additive M1~M10, compares with comparative example S1, can obtain in table 1
Obtain lower voltage platform and higher specific capacity.
Embodiment 11
Positive plate production: additive M6 will be obtained in embodiment 6, positive electrode is incorporated into the ratio of 2wt%
LiNi0.333Co0.333Mn0.333O2It is middle to be used as active material, select SP as conductive agent, PVDF is as binder, with active material
The ratio that+M6:SP:PVDF mass ratio is 96:2:2 is carried out mixing and is mixed into using N-Methyl pyrrolidone (NMP) as solvent
It is applied on aluminium foil after slurry, the slurry after coating is placed in 100 DEG C of vacuum drying ovens and dries 12 hours.
Negative electrode tab production: hard carbon is conductive agent as negative electrode active material, selection SP, and PVDF is binder, with active matter
Matter: conductive agent: the ratio that binder mass ratio is 94:2.5:3.5 carries out mixing, using N-Methyl pyrrolidone (NMP) as molten
Agent is applied on copper foil after being mixed into slurry, and the slurry after coating is placed in 100 DEG C of vacuum drying ovens and dries 12 hours.
The production of non-aqueous batteries: electrolyte selects the 1MLiPF of purchase6As electrolyte, ethylene carbonate (EC) and carbon
Sour second methyl esters (EMC) ratio is the electrolyte of 1:1 volume ratio mixed solvent.Diaphragm selects the commercial polypropylene diaphragm of purchase.
According to soft-package battery structure shown in Fig. 1, it is prepared into soft-package battery.Battery prepared by the embodiment is named as S11.
Embodiment 12~14
Additive M6 will be obtained in embodiment 6, positive electrode is incorporated into the ratio of 4wt%, 6wt%, 8wt% respectively
LiNi0.333Co0.333Mn0.333O2In, soft-package battery is prepared into according to described in embodiment 11.Electricity prepared by 12~14 embodiments
Pond is named as S12~S14.Positive LiNi0.333Co0.333Mn0.333O2The M6 for mixing 4wt%, 6wt%, 8wt% makes with lithium piece
At button half-cell, half-cell charging and discharging curve is shown in Fig. 5.Battery prepared by embodiment 13, charging and discharging capacity-voltage curve are shown in
Fig. 6.
Embodiment 15
The additive M6 that will be obtained in embodiment is incorporated into positive electrode LiNi with the ratio of 7%wt0.8Co0.1Mn0.1O2
In, graphite and silicon oxygen are subjected to mixing as negative electrode active material, according to described in embodiment 11 using the ratio of mass ratio 80:20
Anode and cathode slurry is prepared, and is assembled into soft-package battery.S15 is named as battery prepared by the embodiment.
Embodiment 16
The additive M6 that will be obtained in embodiment is incorporated into positive electrode LiNi with the ratio of 5%wt0.5Co0.3Mn0.2O2
In, graphite and silicon oxygen are subjected to mixing as negative electrode active material, according to described in embodiment 11 using the ratio of mass ratio 80:20
Anode and cathode slurry is prepared, and is assembled into soft-package battery.S16 is named as battery prepared by the embodiment.
Embodiment 17
The additive M6 that will be obtained in embodiment is incorporated into positive electrode LiNi with the ratio of 5%wt0.8Co0.15Al0.05O2
In, cathode selects hard carbon material, according to preparing anode and cathode slurry described in embodiment 11, and is assembled into soft-package battery.For the reality
It applies battery prepared by example and is named as S17.
Comparative example 2
Select LiNi0.333Co0.333Mn0.333O2For positive active material, the incorporation of anode additive is not carried out to it, with
LiNi0.333Co0.333Mn0.333O2: the ratio that SP:PVDF ratio is 96:2:2 carries out mixing, hard carbon as negative electrode active material,
Soft-package battery is prepared in the way of embodiment 11, and names D2, the full electricity of comparative example D2 preparation for the battery of embodiment preparation
The capacitance-voltage curves in pond are shown in Fig. 6.
To embodiment 11~17 and the obtained soft-package battery of comparative example 2, it is tested under 0.05C multiplying power, full battery voltage
Capacity after recycling 100 times under first charge-discharge specific capacity under range 2.6-4.2V, charging and discharging capacity and 1C multiplying power is kept
Rate, test result formula is in following table 2.
Table 2
In table 2, the electric discharge for the first time of full battery is can be improved it has been confirmed that incorporation anode additive in embodiment 11~17
Specific capacity.
The foregoing is merely only a few embodiments of the invention, are not intended to limit the invention, all of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within spirit and principle.
Claims (9)
1. a kind of lithium ion cell positive additive, which is characterized in that its general formula is represented by Li5+aFexAyBzO4, in which: 0≤x
A≤2 < z≤0.1, x+y+z=1,0 < of≤1,0≤y≤1,0.
2. lithium ion cell positive additive according to claim 1, which is characterized in that the A be selected from Co, Mn, Zn, Ir,
Any one or more in Pt, Ni；The B is selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb rare earth member
Any one or more in element.
3. the preparation method of lithium ion cell positive additive described in claim 1, which is characterized in that press atomic molar ratio for lithium
Source, source of iron, transition metal source, rare-earth compound after mixing, are warming up to 700~900 DEG C of heat preservations 2 under protective atmosphere
It is made after~60h.
4. the preparation method of lithium ion cell positive additive according to claim 3, which is characterized in that the lithium source is oxygen
Change lithium, lithium carbonate, lithium nitrate, lithium acetate, lithium oxalate, lithium hydroxide, the combination of one or more of lithium alkylide.
5. the preparation method of lithium ion cell positive additive according to claim 3, which is characterized in that the source of iron is α-
One of iron oxide, beta oxidation iron, ferroso-ferric oxide, ferric sulfate, ferric nitrate, iron hydroxide, iron chloride, ferric acetate are several
Kind.
6. the preparation method of lithium ion cell positive additive according to claim 3, which is characterized in that the transition metal
Source is one of oxidation of interim metal, sulfide, nitride, disulphide, phosphide, hydroxide, chloride
Or it is several.
7. the preparation method of lithium ion cell positive additive according to claim 3, which is characterized in that the rare earth element
Compound is the nitrate of rare earth element, one or more of sulfate, oxide, hydroxide, chloride.
8. a kind of non-aqueous batteries, which is characterized in that including positive active material, negative electrode active material, positive and negative anodes collector, electricity
Solve liquid, diaphragm, tab and aluminum plastic film outer packing.
9. non-aqueous batteries according to claim 8, which is characterized in that the positive active material includes claim 1 institute
Lithium ion cell positive additive is stated, content is 0.01~10%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN110867584B (en) * | 2019-11-04 | 2021-09-21 | 宁德新能源科技有限公司 | Lithium supplement material and positive electrode comprising same |
| CN113839007A (en) * | 2020-06-24 | 2021-12-24 | 深圳市比亚迪锂电池有限公司 | Lithium ion battery anode slurry and lithium ion battery |
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