CN101295780B - Anode active material composition of lithium ion secondary battery and battery - Google Patents
Anode active material composition of lithium ion secondary battery and battery Download PDFInfo
- Publication number
- CN101295780B CN101295780B CN2007100742463A CN200710074246A CN101295780B CN 101295780 B CN101295780 B CN 101295780B CN 2007100742463 A CN2007100742463 A CN 2007100742463A CN 200710074246 A CN200710074246 A CN 200710074246A CN 101295780 B CN101295780 B CN 101295780B
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ion secondary
- secondary battery
- positive electrode
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims description 33
- 239000006183 anode active material Substances 0.000 title claims description 15
- 239000007774 positive electrode material Substances 0.000 claims abstract description 33
- 229910011993 LiFe0.5Co0.5PO4 Inorganic materials 0.000 claims abstract description 11
- 229910013716 LiNi Inorganic materials 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 22
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 description 42
- 239000011572 manganese Substances 0.000 description 30
- 239000000126 substance Substances 0.000 description 25
- 229910052493 LiFePO4 Inorganic materials 0.000 description 24
- 239000002671 adjuvant Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000013078 crystal Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003796 beauty Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a positive active material combination for a lithium ion secondary battery and a lithium ion secondary battery containing the combination. The combination mainly consists of LiFe0.5Co0.5PO4 and LiNi0.75Co0.1Al0.1Mn0.05O2. The LiFe0.5Co0.5PO4 and LiNi0.75Co0.1Al0.1Mn0.05O2 are mixed as the positive active material of the lithium ion secondary battery to ensure that the lithium ion secondary battery of the invention has outstanding high temperature stability, excellent high current cycling capacity holdover performance and excellent safety, thus removing various disadvantages of the lithium ion secondary battery produced by a positive active material which only adopts LiFe0.5Co0.5PO4 and LiNi0.75Co0.1Al0.1Mn0.05O2. The invention can be widely applied to the preparation field of the lithium ion secondary battery, especially power batteries.
Description
[technical field]
The present invention relates to anode active material of lithium ion secondary battery, be specifically related to anode active material composition of lithium ion secondary battery and use the battery of this anode active material composition.
[background technology]
Lithium ion battery is the green battery of a new generation, is considered to 21st century to national economy and the significant new high-tech product of people's lives.Numerous advantages such as lithium ion battery has that voltage height, energy density are big, good cycle, self discharge are little, memory-less effect, operating temperature range are wide, it has been widely used in mobile phone, notebook computer, UPS, video camera, various portable power tool, electronic instrument, weaponry etc. as the high-energy-density chemical power source, also is the electric automobile studied energetically of various countries, the first-selected supporting power supply of space power system.Advanced battery material especially positive electrode has constituted the core technology that present lithium ion battery updates, and is one of key technology of lithium ion battery.
The positive electrode that lithium rechargeable battery uses mainly is an intercalation compounds, and common alternative material mainly contains tertiary cathode material, stratiform cobalt acid lithium, lithium manganate having spinel structure etc.Widely used at present positive electrode is a stratiform cobalt acid lithium material.Stratiform cobalt acid lithium, tertiary cathode material and various derivative thereof (doping by zwitterion or other materials coated etc. mode) are though have higher specific discharge capacity, but their thermal stabilitys under charged state are relatively poor, and cobalt and nickel as raw material cost an arm and a leg, and have the problem of shortage of resources.
CN200610072027.7 mixes tertiary cathode material and use to wish to obtain a kind of excellent combination property, positive electrode with low cost with spinel lithium manganate.But the various performances of this positive electrode such as specific discharge capacity, 100 circulation volume conservation rates, 100 high temperature circulation capability retentions, thermal stabilitys all are lower than every performance (seeing table 1 in the CN200610072027.7 specification) of tertiary cathode material, and the battery specific capacity that contains LiMn2O4 is lower, cycle performance particularly high temperature cyclic performance is relatively poor, lattice instability when discharging and recharging, under strong collision, can produce blast, life security to the consumer constitutes a threat to, and is unfavorable for preparing high-capacity power battery.
LiFePO4 (the LiFePO of olivine-type structure
4) positive electrode becomes new research focus both at home and abroad gradually.Primary Study shows that this novel anode material has been concentrated LiCoO
2, LiNiO
2, LiMnO
2Advantage separately Deng material: do not contain noble element, raw material cheapness, resource are greatly abundant; Operating voltage moderate (3.40V); Platform identity is good, and voltage pole is steady, can match in excellence or beauty with stabilized voltage power supply: theoretical capacity big (170mAh/g); Stability Analysis of Structures, security performance splendid (oxygen atom and phosphorus atoms make material be difficult to analyse oxygen and decompose with the strong covalent bond strong bonded); High-temperature behavior and good cycle; Volume-diminished during charging, the bulk effect when cooperating with carbon negative pole material is good; Good with most of electrolyte system compatibilities, storge quality is good; Nontoxic, be real green material.Yet there are two significant disadvantages in LiFePO4, the one, and conductivity is low, causes high-rate charge-discharge capability poor, and actual specific capacity is low; The 2nd, bulk density is low, causes volume and capacity ratio low.These two shortcomings have hindered the large-scale application of this material.
[summary of the invention]
The objective of the invention is to overcome tertiary cathode material and olivine-type LiFePO4 separately as the limitation of lithium ion secondary battery anode material, and a kind of excellent combination property is provided, anode active material composition of lithium ion secondary battery with low cost, that capacity is high, high-rate charge-discharge capability good, security performance is good and use said composition are as the battery of positive electrode.
For realizing above-mentioned technical purpose, the present invention by the following technical solutions:
A kind of anode active material composition of lithium ion secondary battery, it is mainly by LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2And LiFe
0.5Co
0.5PO
4Form.
In the above-mentioned anode active material composition of lithium ion secondary battery, described LiFe
0.5Co
0.5PO
4With LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Weight ratio be 1～9: 9～1.
In the above-mentioned anode active material composition of lithium ion secondary battery, described LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2With LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Weight ratio preferred 4～6: 6～4.
A kind of lithium rechargeable battery comprises positive pole, negative pole, electrolyte and barrier film, it is characterized in that: described positive electrode active materials is mainly by LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2And LiFe
0.5Co
0.5PO
4Form.
In the above-mentioned lithium rechargeable battery, LiFe in the described positive electrode
0.5Co
0.5PO
4With LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Weight ratio be 1～9: 9～1.
In the above-mentioned lithium rechargeable battery, LiFe in the described positive electrode
0.5Co
0.5PO
4With LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Weight ratio preferred 4～6: 6～4.
Adopt technique scheme, compared with prior art, the useful technique effect that is produced is: the limitation when it has overcome tertiary cathode material and olivine-type LiFePO4 separately as lithium ion secondary battery anode material.The poor heat stability of tertiary cathode material, heavy-current discharge performance are also poor, and the olivine-type LiFePO4 has the removal lithium embedded function, and it has concentrated LiCoO
2, LiNiO
2, LiMnO
2Advantage Deng material: operating voltage is moderate, platform identity is good, self-discharge rate is extremely low, its crystal structure has determined it in the embedding of lithium ion/take off in the embedding process, volume can not change basically, and the embedding of lithium ion and deviate from the influence of lattice not quite has good invertibity, voltage pole is steady, can match in excellence or beauty with stabilized voltage power supply; Oxygen atom and phosphorus atoms be with the strong covalent bond strong bonded in the crystal structure, makes material be difficult to analyse oxygen and decompose and make its Stability Analysis of Structures, and security performance is splendid; High-temperature behavior and good cycle can reach 2000 times; Volume-diminished during charging, the bulk effect when cooperating with carbon negative pole material is good; Good with most electrolyte system compatibilities, storge quality is good.The LiNi that the mode such as coated of the tertiary cathode material of volume contraction and the doping by zwitterion or other materials obtained when volume became big, discharge when the present invention will charge
0.75Co
0.1Al
0.1Mn
0.05O
2Volume-diminished when adding charging to, volume becomes big LiFe during discharge
0.5Co
0.5PO
4Middle one side can realize composition volume complementation when discharging and recharging, it is constant substantially that thereby cumulative volume keeps, be equivalent to LiFePO4 coated with conductive material on the other hand, mix and carry out electrode modification, make the electronic and ionic conductivity of LiFePO4 increase, overcome it and be not suitable for the defective of high current charge-discharge.Experimental result proof LiFe
0.5Co
0.5PO
4With LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Both mix use can effectively overcome separately shortcoming, has inherited the high advantage of both capacity again simultaneously, obviously improves thermal stability, resistance to elevated temperatures and the specific capacity of material, prolongs its cycle life and increases big current cycle discharge capacitance.In addition, LiFe
0.5Co
0.5PO
4Price comparatively cheap, so can effectively reduce cost.
[embodiment]
The invention discloses a kind of anode active material composition of lithium ion secondary battery, mainly form by tertiary cathode material and olivine-type LiFePO4, limitation when purpose is to overcome tertiary cathode material and olivine-type LiFePO4 separately as positive electrode, inherit both advantages separately simultaneously, thereby make the battery excellent combination property that makes by combined material, with low cost, capacity is high, high-rate charge-discharge capability good.
In the above-mentioned anode active material composition of lithium ion secondary battery, the chemical general formula of described tertiary cathode material is Li
a(Ni
bCo
c) M
1-b-cO
2, 0.97≤a≤1.07,0＜b＜1,0＜c＜1,0.5≤b+c＜1 wherein, M is at least a in aluminium (Al), manganese (Mn), iron (Fe), titanium (Ti), zinc (Zn), calcium (Ca), chromium (Cr) and the copper (Cu).
In the above-mentioned lithium rechargeable battery, the chemical general formula of olivine-type LiFePO4 described in the described positive electrode is LiFe
xM '
1-xPO4 (0＜x≤1) wherein M ' can be cobalt, manganese, magnesium or titanium.
In the above-mentioned anode active material composition of lithium ion secondary battery, the weight ratio of described olivine-type LiFePO4 and tertiary cathode material is 1～9: 9～1, preferred 4～6: 6～4.
The present invention also discloses a kind of lithium rechargeable battery, comprises positive pole, negative pole, electrolyte and barrier film, it is characterized in that: described positive electrode active materials is made up of tertiary cathode material and olivine-type LiFePO4 basically.
In the above-mentioned lithium rechargeable battery, the chemical general formula of tertiary cathode material described in the described positive electrode is Li
a(Ni
bCo
c) M
1-b-cO
2, 0.97≤a≤1.07,0＜b＜1,0＜c＜1,0.5≤b+c＜1 wherein, M is at least a in aluminium (Al), manganese (Mn), iron (Fe), titanium (Ti), zinc (Zn), calcium (Ca), chromium (Cr) and the copper (Cu).
In the above-mentioned lithium rechargeable battery, the chemical general formula of olivine-type LiFePO4 described in the described positive electrode is LiFe
xM '
1-xPO4 (0＜x≤1) wherein M ' can be cobalt, manganese, magnesium or titanium.
In the above-mentioned lithium rechargeable battery, the weight ratio of olivine-type LiFePO4 and tertiary cathode material is 1～9: 9～1 in the described positive electrode.
In the above-mentioned lithium rechargeable battery, the weight ratio of olivine-type LiFePO4 and tertiary cathode material preferred 4～6 in the described positive electrode: 6～4.
Use by tertiary cathode material and olivine-type LiFePO 4 material are mixed, overcome tertiary cathode material and olivine-type LiFePO4 separately as the limitation of positive electrode.Because the poor heat stability of tertiary cathode material, heavy-current discharge performance is also poor, and the high-temperature behavior of olivine-type LiFePO4 is good, and heavy-current discharge is stable, and both mix use can effectively overcome separately shortcoming, inherits the high advantage of both capacity simultaneously.In addition, the price of olivine-type LiFePO4 is comparatively cheap, can effectively reduce cost.
According to the following example, technical conceive that can better understand the present invention and advantage.
Embodiment 1
At first getting chemical formula is LiNi
1/3Mn
1/3Co
1/3O
2Tertiary cathode material and chemical formula be LiFePO
4The olivine-type LiFePO4, the two mass ratio is 9: 1, and both are mixed as positive electrode active materials.With PVDF is adhesive, and its quality is 4% of a positive electrode active materials quality, is conductive agent with acetylene black, and its quality is 2% of a positive electrode active materials quality, is solvent with NMP, and its quality is 50% of a positive electrode active materials quality.Positive electrode active materials, adhesive, acetylene black and NMP are mixed, under the speed of 6000rpm, stirred 5 hours, make it even dispersion.Pass through operations such as coating, oven dry, compressing tablet then, make the positive plate material.Wherein mix, be coated with, dry three processes and all need under vacuum environment, carry out, the positive plate material that obtains behind the compressing tablet according to the specified size cutting, is made positive plate.
Adopt the prior art for preparing negative pole.With carbon dust and acetylene black is conductive agent, is bonding agent with CMC, is solvent with water, adds an amount of SBR again, mix, and coating, oven dry, compressing tablet makes negative plate after being cut into specified size.
The positive plate that adopts said method to make, negative plate, with LiPF6 is electrolyte, mixture with vinyl carbonate, ethylene carbonate and diethyl carbonate is a solvent, its concentration is 1.2 mol, adopt polyethylene polypropylene composite diaphragm paper, make lithium rechargeable battery of the present invention by common process.
The lithium rechargeable battery that is assembled into by above-mentioned positive plate, negative plate, electrolyte and barrier film has advantage with low cost, that capacity is high, high-rate charge-discharge capability is good.
Embodiment 2
It is LiNi that present embodiment adopts chemical formula
0.1Mn
0.1Co
0.8O
2Tertiary cathode material and crystal structure be the LiFe of olivine-type
0.2Mn
0.8PO
4Mixture as positive electrode active materials, the two mass ratio is 1: 9, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1.
Embodiment 3
It is LiNi that present embodiment adopts chemical formula
0.4Mn
0.2Co
0.4O
2Tertiary cathode material and crystal structure be the LiFe of olivine-type
0.8Mg
0.2PO
4Mixture as positive electrode active materials, the two mass ratio is 4: 6, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1.
Embodiment 4
It is LiNi that present embodiment adopts chemical formula
0.75Co
0.1Al
0.1Mn
0.05O
2Tertiary cathode material and crystal structure be the LiFe of olivine-type
0.5Co
0.5PO
4Mixture as positive electrode active materials, the two mass ratio is 6: 4, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1.
Embodiment 5
It is LiNi that present embodiment adopts chemical formula
0.4Co
0.1Mn
0.4Al
0.05Fe
0.05O
2Tertiary cathode material and crystal structure be the LiFe of olivine-type
0.2Mn
0.8PO
4Mixture as positive electrode active materials, the two mass ratio is 2: 8, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1.
Embodiment 6
It is LiNi that present embodiment adopts chemical formula
0.7Co
0.15Mn
0.1Ti
0.03Cu
0.02O
2Tertiary cathode material and crystal structure be the LiFe of olivine-type
0.8Mg
0.2PO
4Mixture as positive electrode active materials, the two mass ratio is 7: 3, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1.
Embodiment 7
It is LiNi that present embodiment adopts chemical formula
0.8Co
0.1Mn
0.05Al
0.02Cr
0.02Ti
0.01O
2Tertiary cathode material and crystal structure be the LiFe of olivine-type
0.2Mn
0.8PO
4Mixture as positive electrode active materials, the two mass ratio is 6: 4, the preparation of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1.
Embodiment 8
It is Li (Ni that present embodiment adopts chemical formula
1/3Co
1/3Mn
1/3)
0.95Zn
0.02Ca
0.01Ti
0.02O
2Tertiary cathode material and crystal structure be the LiFe of olivine-type
0.5Co
0.5PO
4Mixture as positive electrode active materials, the two mass ratio is 5: 5, the preparation of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1.
Embodiment 9
It is Li that present embodiment adopts chemical formula
0.97Ni
0.51Mn
0.25Co
0.24O
2Tertiary cathode material and crystal structure be the LiFePO of olivine-type
4Mixture as positive electrode active materials, the two mass ratio is 8: 2, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1.
Embodiment 10
It is Li that present embodiment adopts chemical formula
1.07Ni
0.25Mn
0.27Co
0.48O
2Tertiary cathode material and crystal structure be the LiFe of olivine-type
0.2Mn
0.8PO
4Mixture as positive electrode active materials, the two mass ratio is 4: 6, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1.
Embodiment 11
It is LiNi that present embodiment adopts chemical formula
1/3Mn
1/3Co
1/3O
2Tertiary cathode material and crystal structure be the LiFe of olivine-type
0.1Ti
0.9PO
4Mixture as positive electrode active materials, the two mass ratio is 5: 5, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1.
Comparative Examples 1
To select chemical formula for use be LiNi to positive electrode active materials in this Comparative Examples
1/3Mn
1/3Co
1/3O
2Tertiary cathode material, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1
Comparative Examples 2
To select chemical formula for use be LiFePO to positive electrode active materials in this Comparative Examples
4The olivine-type LiFePO4, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 1.
Comparative Examples 3
To select chemical formula for use be LiNi to positive electrode active materials in this Comparative Examples
0.1Mn
0.1Co
0.8O
2Tertiary cathode material, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 2.
Comparative Examples 4
To select chemical formula for use be LiFe to positive electrode active materials in this Comparative Examples
0.2Mn
0.8PO
4Tertiary cathode material, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 2.
Comparative Examples 5
To select chemical formula for use be LiNi to positive electrode active materials in this Comparative Examples
0.4Mn
0.2Co
0.4O
2Tertiary cathode material, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 3.
Comparative Examples 6
To select chemical formula for use be LiFe to positive electrode active materials in this Comparative Examples
0.8Mg
0.2PO
4Tertiary cathode material, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 3.
Comparative Examples 7
To select chemical formula for use be LiNi to positive electrode active materials in this Comparative Examples
0.75Co
0.1Al
0.1Mn
0.05O
2Tertiary cathode material, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 4.
Comparative Examples 8
To select chemical formula for use be LiFe to positive electrode active materials in this Comparative Examples
0.5Co
0.5PO
4Tertiary cathode material, the preparation process of other ratio of adjuvant and positive plate, negative plate and lithium ion battery is with embodiment 4.
The performance of lithium-ion secondary battery test
Lithium rechargeable battery to embodiment and Comparative Examples preparation carries out performance test, and test result sees Table 1.
Table 1 adopts the performance of the lithium rechargeable battery of different positive electrode active materials
Can see by table 1, compare as the lithium rechargeable battery of positive electrode active materials preparation with the employing tertiary cathode material, 300 circulation backs of 300 loop tests of the big electric current of lithium rechargeable battery 1C of various embodiments of the present invention preparation and the big electric current of 5C discharge capacitance is bigger, and its high-temperature stability is stronger.By regulating the kind and the proportioning of tertiary cathode material and olivine-type LiFePO4, the discharge capacitance after the big electric current of lithium rechargeable battery 5C of the present invention circulates for 300 times is higher than with the conservation rate of olivine-type LiFePO4 as 300 circulation backs of the big electric current of 5C discharge capacity of the lithium rechargeable battery of positive electrode active materials.Explanation can overcome the defective of tertiary cathode material poor heat stability and olivine-type lithium iron phosphate high multiplying charge-discharge performance difference under charged state as the positive electrode active materials of lithium rechargeable battery with the mixture of olivine-type LiFePO4 and tertiary cathode material, realize the complementation of tertiary cathode material and olivine-type LiFePO4 performance, thereby the performance of battery is greatly improved.
Claims (6)
1. an anode active material composition of lithium ion secondary battery is characterized in that, by LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2And LiFe
0.5Co
0.5PO
4Form.
2. according to each described anode active material composition of lithium ion secondary battery of claim 1, it is characterized in that: described LiFe
0.5Co
0.5PO
4With LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Weight ratio be 1～9: 9～1.
3. anode active material composition of lithium ion secondary battery according to claim 2 is characterized in that: described LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2With LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Weight ratio be 4～6: 6～4.
4. a lithium rechargeable battery comprises positive pole, negative pole, electrolyte and barrier film, it is characterized in that: described positive electrode active materials is by LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2And LiFe
0.5Co
0.5PO
4Form.
5. lithium rechargeable battery according to claim 4 is characterized in that: LiFe in the described positive electrode
0.5Co
0.5PO
4With LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Weight ratio be 1～9: 9～1.
6. lithium rechargeable battery according to claim 5 is characterized in that: LiFe in the described positive electrode
0.5Co
0.5PO
4With LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Weight ratio be 4～6: 6～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100742463A CN101295780B (en) | 2007-04-28 | 2007-04-28 | Anode active material composition of lithium ion secondary battery and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100742463A CN101295780B (en) | 2007-04-28 | 2007-04-28 | Anode active material composition of lithium ion secondary battery and battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101295780A CN101295780A (en) | 2008-10-29 |
| CN101295780B true CN101295780B (en) | 2011-08-10 |
Family
ID=40065905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100742463A Active CN101295780B (en) | 2007-04-28 | 2007-04-28 | Anode active material composition of lithium ion secondary battery and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101295780B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010051748A1 (en) * | 2008-11-07 | 2010-05-14 | Byd Company Limited | Cathode active material, lithium ion secondary battery and rechargeable battery having the same |
| CN102386409A (en) * | 2011-11-03 | 2012-03-21 | 湖南丰源业翔晶科新能源股份有限公司 | Paste for cathode of lithium iron phosphate lithium ion battery |
| CN103618084A (en) * | 2013-11-21 | 2014-03-05 | 刘铁建 | Mixed positive material of lithium-ion power battery |
| CN105470494A (en) * | 2014-08-29 | 2016-04-06 | 比亚迪股份有限公司 | Active material composition for positive electrode, positive electrode slurry and preparation method thereof, positive plate and preparation method thereof, and lithium ion battery |
| CN105514354A (en) * | 2015-12-16 | 2016-04-20 | 上海航天电源技术有限责任公司 | Power lithium ion battery and positive plate and preparing method thereof |
| CN106328935A (en) * | 2016-08-30 | 2017-01-11 | 合肥国轩高科动力能源有限公司 | Composite system power battery with high safety and long service life and preparation method of composite system power battery |
| CN109761210A (en) * | 2018-12-13 | 2019-05-17 | 天津力神电池股份有限公司 | The preparation method of iron manganese phosphate for lithium and its method for coating ternary material |
| CN112563508A (en) * | 2020-12-10 | 2021-03-26 | 杭州肄康新材料有限公司 | Lithium ion battery anode material, lithium ion battery anode and lithium ion battery |
| CN117117292A (en) * | 2023-08-08 | 2023-11-24 | 湖南恒优能科技有限公司 | Low-resistance Wen Tieli battery device structure and manufacturing method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1949563A (en) * | 2006-10-26 | 2007-04-18 | 复旦大学 | High safety performance lithium ion cell and preparing method thereof |
-
2007
- 2007-04-28 CN CN2007100742463A patent/CN101295780B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1949563A (en) * | 2006-10-26 | 2007-04-18 | 复旦大学 | High safety performance lithium ion cell and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2006-134770A 2006.05.25 |
| JP特开2006-332020A 2006.12.07 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101295780A (en) | 2008-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109935783B (en) | Electrochemical device and electronic device | |
| CN101295780B (en) | Anode active material composition of lithium ion secondary battery and battery | |
| CN102903914B (en) | Active substance, its manufacture method, electrode, secondary cell and set of cells | |
| US20140087257A1 (en) | Cathode material and lithium ion battery therefrom | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| KR102502618B1 (en) | Secondary battery, battery module including secondary battery, battery pack and device | |
| CN106058245A (en) | Low temperature lithium ion battery | |
| AU2011230912B2 (en) | Active material for battery, and battery | |
| CN106602129A (en) | Multi-ion battery and preparation method thereof | |
| CN111342137A (en) | Electrolyte and electrochemical device | |
| CN102629686A (en) | Electrode material of drainage rechargeable and dischargeable lithium ion and aqueous solution rechargeable and dischargeable lithium ion battery | |
| CN102427123A (en) | Lithium ion secondary battery and anode sheet thereof | |
| CN115411346A (en) | Lithium ion battery and electrochemical device comprising same | |
| CN101651198B (en) | Doping lithium iron phosphate material and preparation method and application thereof | |
| WO2022198651A1 (en) | Positive electrode plate, and electrochemical device and electronic device containing positive electrode plate | |
| CN100453454C (en) | Preparation method of lithium ferrous phosphate positive electrode material | |
| EP3965201A1 (en) | Secondary battery and device containing same | |
| WO2021189425A1 (en) | Secondary cell, and device comprising secondary cell | |
| JP7432607B2 (en) | Positive electrode piece, electrochemical device and electronic device including the positive electrode piece | |
| CN113748549B (en) | Secondary battery and device containing the same | |
| CN116130651A (en) | Pole piece, lithium ion battery, battery module, battery pack and electricity utilization device | |
| CN103137958B (en) | A kind of modification vanadic oxide positive electrode and methods for making and using same thereof | |
| CN114094188B (en) | Electrochemical device and electronic device comprising same | |
| CN116960466B (en) | Electrolyte, secondary battery and electricity utilization device | |
| WO2024082123A1 (en) | Electrolyte solution, secondary battery, battery module, battery pack, and electric device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160826 Address after: Kwai Chung street Beek Industrial Park in Longgang District of Shenzhen City, Guangdong Province, No. 6 building 518000 Patentee after: SHENZHEN BAK POWER BATTERY Co.,Ltd. Address before: Kwai Chung street Beek Industrial Park in Longgang District of Shenzhen City, Guangdong province 518119 Patentee before: SHENZHEN BAK BATTERY Co.,Ltd. |
|
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20191022 Granted publication date: 20110810 |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20221022 Granted publication date: 20110810 |
|
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20221022 Granted publication date: 20110810 |